Oligomeric polyol compositions

ABSTRACT

There is provided an oligomeric polyol composition having (a) an oligomeric network containing residues of at least one polyhydroxylated aromatic compound and residues of at least one polyol having at least three hydroxyl groups; and (b) a plurality of peripheral groups having one or more pendant hydroxyl groups bound to the oligomeric network by a plurality of linking units. The residues of the polyol may optionally contain one or more oxygen ether groups, one or more amino ether groups, or both one or more oxygen ether groups and one or more amino ether groups. Reaction of the oligomeric polyols with isocyanate monomers affords a new class of polyurethanes having superior heat and water resistance. The new polyurethanes exhibit lower peak exotherms, typically less than 250° F. during in-mold polymerization. Articles prepared from polyurethanes incorporating such oligomeric polyol compositions exhibit flexural strengths and moduli in excess of 10,000 psi and 400,000 psi respectively, and outstanding green strength.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from US Provisional Application Ser.No. 62/485,000 filed Apr. 13, 2017.

BACKGROUND

This disclosure relates to oligomeric compositions useful in thepreparation of polymeric compositions. In particular, this disclosurerelates to oligomeric polyol compositions useful in the preparation ofpolyurethane compositions.

Polyurethanes are important industrial polymers used in a wide varietyof applications including rigid and flexible foams, thermoplastic andthermosetting elastomers, sealants, coatings and adhesives, elastomericfibers, and synthetic leather-like materials. Most polyurethanes usedcommercially are elastomers with Young's moduli less than about 50,000psi, but some polyurethanes in unfilled form have moduli ranging from250,000 psi to 500,000 psi or more. Examples include TPU engineeringplastics (Isoplast®) and a number of commercial cast systems.Polyurethanes have several shortcomings including the need for moldrelease agents, long demold times (poor green strength) and intensein-mold exotherms that can cause visual imperfections in the final part.Such imperfections include color change and surface splay fromoutgassing. Most polyurethane elastomers are generally not used forstructural applications due to their typical low modulus and strength.The flexural moduli of most polyurethane compositions are well below300,000 psi and flexural strength values are typically below 10,000 psi.Known polyurethanes may be deficient in terms of their resistance toheat, and are frequently characterized by heat distortion temperatureswhich are less than 100 degrees centigrade. In addition, upon exposureto conditions of high humidity at moderate temperature knownpolyurethanes may exhibit significant loss of material properties.

U.S. Pat. No. 8,110,710 discloses the reaction of bisphenol Apolycarbonate with aliphatic diols to produce a mixture of bisphenol Ahydroxy alkylene ethers and free bisphenol A. The reference does notdisclose the formation of oligomeric polyols comprising an oligomericnetwork comprising residues of at least one polyhydroxylated aromaticcompound and residues of at least one polyol having at least threehydroxyl groups.

Non-patent reference Process Safety and Environmental Protection, Volume100, Pages 281-287, 2016 discloses the reaction of bisphenol Apolycarbonate with glycerol to produce a mixture of free bisphenol A andthe mono and diglycerol ethers of bisphenol A. The reference does notdisclose the formation of oligomeric polyols comprising an oligomericnetwork comprising residues of at least one polyhydroxylated aromaticcompound and residues of at least one polyol having at least threehydroxyl groups.

International Application WO 2015/132080 A1 discloses the reaction of2-hydroxyethyl 2-oxo-1,3-dioxolane-4-carboxylate with an oligomer of themono-glycidyl ether of bisphenol A to provide an adduct comprising twoterminal residues of 2-hydroxyethyl 2-oxo-1,3-dioxolane-4-carboxylatewhich is subsequently reacted with a diamine to produce a linearpolyurethane. The reference does not disclose the formation ofoligomeric polyols comprising an oligomeric network comprising residuesof at least one polyhydroxylated aromatic compound and residues of atleast one polyol having at least three hydroxyl groups. Nor does thereference disclose a polyurethane prepared from such an oligomericpolyol and advantages attendant the incorporation of such oligomericpolyols into highly crosslinked polyurethanes.

Thus, there is a need for new polyurethane compositions which exhibitsuperior heat resistance, enhanced stability in the presence of water,improved strength, hardness, and molding characteristics relative toknown polyurethane materials. There is a need for starting materialsuseful in preparing polyurethane based compositions which exhibitsuperior heat resistance, enhanced stability in the presence of water,improved strength, hardness, and molding characteristics relative toknown polyurethane materials.

BRIEF DESCRIPTION

This disclosure addresses many of the shortcomings of knownpolyurethanes by providing novel oligomeric polyol compositions, whichwhen reacted with isocyanate monomers or functional equivalents thereofprovide a new class of polyurethanes having superior heat resistance andsuperior resistance to water. The polyurethane compositions disclosedherein may exhibit heat distortion temperatures in excess of 110 degreescentigrade, and essentially no loss of material properties in prolongedhumidity tests at 70 degrees centigrade. The new polyurethanes exhibitlower peak exotherms, typically less than 250 degrees Fahrenheit duringin-mold curing/polymerization. In addition, articles prepared frompolyurethanes incorporating such oligomeric polyol compositions asreactants exhibit flexural strengths in excess of 10,000 psi andflexural moduli in excess of 400,000 psi, and exhibit outstanding greenstrength.

Disclosed is an oligomeric polyol composition comprising: (a) anoligomeric network comprising residues of at least one polyhydroxylatedaromatic compound and residues of at least one polyol having at leastthree hydroxyl groups; and (b) a plurality of peripheral groupscomprising one or more pendant hydroxyl groups bound to the oligomericnetwork by a plurality of linking units; wherein the residues of the atleast one polyol may comprise one or more internal functional groupscontaining a heteroatom. The one or more internal functional groupscontaining a heteroatom may comprise one or more oxygen ether groups,one or more amino ether groups, or both of one or more oxygen ethergroups and one or more amino ether groups. The polyhydroxylated aromaticcompound is a compound containing at least one aromatic ring and atleast two hydroxyl groups each bonded directly to an aromatic ring ofsuch compound; the pendant hydroxyl groups are disposed on theoligomeric polyol at a location where they are capable of reacting withany functional group reactive with a hydroxyl group. The functionalgroup reactive with a hydroxyl group may be an isocyanate group. Aportion of the at least one polyhydroxylated aromatic compounds maycomprise at least one aromatic bisphenol. The linking units may beoxygen atoms of hydrocarbyl ether linkages, carbonate moieties, carbonylmoieties, ester moieties, or amino ether moieties

Disclosed is an oligomeric polyol composition comprising: (a) anoligomeric network comprising residues of at least one aromaticbisphenol and residues of at least one polyol having at least threehydroxyl groups; and (b) a plurality of peripheral groups bound to theoligomeric network by a plurality of linking units, the peripheralgroups comprising one or more pendant hydroxyl groups; wherein theresidues of the at least one monomeric polyol may comprise one or moreinternal functional groups containing a heteroatom. The one or moreinternal functional groups containing a heteroatom may comprise one ormore oxygen ether groups, one or more amino ether groups, or one or moreoxygen ether groups and one or more amino ether groups.

Disclosed is an oligomeric polyol composition comprising: (a) anoligomeric network comprising residues of at least one polyhydroxylatedaromatic compound and residues of at least one polyol having at leastthree hydroxyl groups and residues of at least one polyhydroxylatedamine; and (b) a plurality of peripheral groups having one or morependant hydroxyl groups bound to the oligomeric network by a pluralityof linking units; wherein the residues of the at least one polyol andthe at least one polyhydroxylated amine may comprise one or moreinternal functional groups containing a heteroatom. The one or moreinternal functional groups containing a heteroatom may comprise one ormore oxygen ether groups, one or more amino ether groups, or both one ofor more oxygen ether groups and one or more amino ether groups.

Disclosed is an oligomeric polyol composition comprising: (a) anoligomeric network comprising residues of at least one aromaticbisphenol and residues of at least one monomeric polyol having at leastthree hydroxyl groups and residues of at least one polyhydroxylatedamine; and (b) a plurality of peripheral groups bound to the oligomericnetwork by a plurality of linking units, the peripheral groupscomprising one or more pendant hydroxyl groups; wherein the residues ofthe at least one monomeric polyol may comprise one or more oxygen ethergroups, one or more amino ether groups, or both one or more oxygen ethergroups and one or more amino ether groups; and wherein the residues ofat least one polyhydroxylated amine may comprise one or more oxygenether groups.

Disclosed is a method of making an oligomeric polyol compositioncomprising: contacting one or more compositions containing one or morepolyhydroxylated aromatic moieties with one or more polyol moieties inthe presence of at least one activating agent and an effective amount ofat least one of a catalyst, a promoter or a mixture thereof, at atemperature sufficient to cause formation of an oligomeric networkcomprising residues of at least one polyhydroxylated aromatic compoundsand residues of at least one polyol to provide a product oligomericpolyol composition.

Disclosed is a method of making an oligomeric polyol compositioncomprising: contacting one or more aromatic bisphenol moieties with oneor more polyol moieties in the presence of at least one activating agentand an effective amount of at least one of a catalyst, a promoter or amixture thereof, at a temperature sufficient to cause formation of anoligomeric network comprising residues of at least one aromaticbisphenol and residues of at least one polyol to provide a productoligomeric polyol composition.

Disclosed is an oligomeric polyol composition prepared by a methodcomprising: contacting one or more polyhydroxylated aromatic moietieswith one or more polyol moieties in the presence of at least oneactivating agent and an effective amount of at least one of a catalyst,a promoter or a mixture thereof, at a temperature sufficient to causeformation of an oligomeric network comprising residues of at least onepolyhydroxylated aromatic and residues of at least one polyol to providea product oligomeric polyol composition.

Disclosed is an oligomeric polyol composition prepared by a methodcomprising: contacting one or more aromatic bisphenol moieties with oneor more polyol moieties in the presence of at least one activating agentand an effective amount of at least one of a catalyst, a promoter or amixture thereof, at a temperature sufficient to cause formation of anoligomeric network comprising residues of at least one aromaticbisphenol and residues of at least one monomeric polyol to provide aproduct oligomeric polyol composition.

Disclosed is a polyurethane composition prepared from one or morepolyisocyanates and at least one oligomeric polyol compositioncomprising an oligomeric network comprising residues of at least onepolyhydroxylated aromatic compound and residues of at least one polyolhaving at least three hydroxyl groups having a plurality of peripheralgroups bound to the oligomeric network by a plurality of linking units,the peripheral groups comprising one or more pendant hydroxyl groups;wherein urethane units are formed from the isocyanate moieties and thependant hydroxyl groups.

Disclosed is a polyurethane composition prepared from one or morepolyisocyanates and at least one oligomeric polyol compositioncomprising an oligomeric network comprising residues of at least onearomatic bisphenol compound and residues of at least one polyol havingat least three hydroxyl groups having a plurality of peripheral groupsbound to the oligomeric network by a plurality of linking units, theperipheral groups comprising one or more pendant hydroxyl groups;wherein urethane units are formed from the isocyanate moieties and thependant hydroxyl groups.

Disclosed is an article comprising one or more polyurethane compositionsdisclosed herein. Disclosed is a molded article comprising one or morepolyurethane compositions disclosed herein. Disclosed is method ofmaking a polyurethane composition comprising contacting one or morepolyisocyanates with one or more oligomeric polyol compositionscomprising (a) an oligomeric network comprising residues of at least onepolyhydroxylated aromatic compound and residues of at least one polyolhaving at least three hydroxyl groups and (b) a plurality of peripheralgroups bound to the oligomeric network by a plurality of linking units,the peripheral groups comprising one or more pendant hydroxyl groups,optionally in the presence of a catalyst, at a temperature sufficient tocause at least a portion of the pendant hydroxyl groups of theperipheral groups to react with one or more isocyanate groups or latentisocyanate groups of the polyisocyanate moieties to form a polyurethaneproduct.

Disclosed is a method of making a polyurethane composition comprisingcontacting one or more polyisocyanate moieties with one or moreoligomeric polyol compositions comprising (a) an oligomeric networkcomprising residues of at least one aromatic bisphenol and residues ofat least one monomeric polyol having at least three hydroxyl groups and(b) a plurality of peripheral groups bound to the oligomeric network bya plurality of linking units, the peripheral groups comprising one ormore pendant hydroxyl groups, optionally in the presence of a catalyst,at a temperature sufficient to cause at least a portion of the pendanthydroxyl groups of the peripheral groups to react with one or moreisocyanate groups or latent isocyanate groups of the polyisocyanatemoieties to form a polyurethane product.

There is disclosed a method of making a molded article comprising: (a)mixing a first reactant comprising one or more polyisocyanates or latentpolyisocyanates with a second reactant comprising an oligomeric polyolcomposition as disclosed herein; (b) transferring the reactive mixtureinto a mold; and (c) curing the reactive mixture within the mold toafford a molded article.

The polyurethane materials provided by this disclosure are well suitedfor use in the manufacture of structural and semi-structural vehicleparts such as automotive and heavy truck body panels, floor panels,brackets, bumper covers, footsteps and housings, and interior parts suchas door panels, arm rests, center console bodies and covers, cup holdersand similar parts. Other applications include the use of thepolyurethanes in the manufacture of structural and semi-structuralagricultural equipment components such as tractor body parts, brackets,grilles, fan shrouds and the like, and building and construction andindustrial infrastructural pieces such as decks and railings, buildingtrim, window lineals, manhole covers and electrical boxes. Furtherapplications include manufacture of aquatic sports equipment such askayaks, canoes, personal watercraft such as jet skis, paddle boards,surf boards, and light weight fishing craft.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a photograph of a molded polyurethane article comprising anovel oligomeric polyol composition PEP450/9181/PC105.

FIG. 2 is a photograph of a molded polyurethane article comprisingcomponents PEP450/9181 but not containing oligomeric polyol compositionPEP450/9181/PC105.

FIG. 3 is a side by side comparison of the molded polyurethane articlesof FIG. 1 and FIG. 2.

DETAILED DESCRIPTION

The explanations and illustrations presented herein are intended toacquaint others skilled in the art with the disclosure, its principles,and its practical application. The specific embodiments of the presentdisclosure as set forth are not intended as being exhaustive or limitingof the disclosure. The scope of the disclosure should, therefore, bedetermined not with reference to the above description, but shouldinstead be determined with reference to the appended claims, along withthe full scope of equivalents to which such claims are entitled. Thedisclosures of all articles and references, including patentapplications and publications, are incorporated by reference for allpurposes. Other combinations are also possible as will be gleaned fromthe following claims, which are also hereby incorporated by referenceinto this written description.

One or more as used herein means that at least one, or more than one, ofthe recited components may be used as disclosed. Nominal as used withrespect to functionality means the theoretical functionality. This canbe calculated from the stoichiometry of the ingredients used. The actualfunctionality may be different due to imperfections in raw materials,incomplete conversion of the reactants and formation of by-products.Durability in this context means that the composition once cured remainssufficiently strong to perform its designed function Residual content ofa component refers to the amount of the component present in free formor reacted with another material, such as an adduct, oligomer or a curedproduct. The residual content of a component can be calculated from theingredients utilized to prepare the component or composition. It may bedetermined utilizing known analytical techniques. Heteroatom meansnitrogen, oxygen, sulfur, silicon, selenium and phosphorus, heteroatomsmay include nitrogen and oxygen. Hydrocarbyl as used herein refers to agroup containing one or more carbon atom backbones and hydrogen atoms,which may optionally contain one or more heteroatoms. As used herein,the term “hydrocarbyl” refers an organic radical which may be any of anaromatic radical, a cycloaliphatic radical, or an aliphatic radical asthose terms are defined herein. Where the hydrocarbyl group containsheteroatoms, the heteroatoms may form one or more functional groups wellknown to one skilled in the art. Hydrocarbyl groups may containcycloaliphatic, aliphatic, aromatic or any combination of such segments.The aliphatic segments can be straight or branched. The aliphatic andcycloaliphatic segments may include one or more double and/or triplebonds. Included in hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl,cycloalkyl, cycloalkenyl, alkaryl and aralkyl groups. Cycloaliphaticgroups may contain both cyclic portions and noncyclic portions.Hydrocarbylene means a hydrocarbyl group or any of the described subsetshaving more than one valence, such as alkylene, alkenylene, alkynylene,arylene, cycloalkylene, cycloalkenylene, alkarylene and aralkylene. Asused herein percent by weight or parts by weight refer to, or are basedon, the weight of the disclosed compositions unless otherwise specified.

The term isocyanate-reactive compound as used herein includes anyorganic compound having nominally greater than one, or at least two,isocyanate-reactive moieties. For the purposes of this invention, anactive hydrogen containing moiety refers to a moiety containing ahydrogen atom which, because of its position in the molecule, displayssignificant activity according to the Zerewitinoff test described byWohler in the Journal of the American Chemical Society, Vol. 49, p. 3181(1927). Illustrative of such isocyanate reactive moieties, such asactive hydrogen moieties, are —COOH, —OH, —NH₂, —NH—, —CONH₂, —SH, and—CONH—. Preferable active hydrogen containing compounds include polyols,polyamines, polymercaptans and polyacids. More preferably, theisocyanate reactive compound is a polyol, and is even more preferably apolyether polyol.

As used herein, the term “aromatic radical” refers to an array of atomshaving a valence of at least one comprising at least one aromatic group.The array of atoms having a valence of at least one comprising at leastone aromatic group may include heteroatoms, or may be composedexclusively of carbon and hydrogen. As used herein, the term “aromaticradical” includes but is not limited to phenyl, pyridyl, furanyl,thienyl, naphthyl, phenylene, and biphenyl radicals. As noted, thearomatic radical contains at least one aromatic group. The aromaticgroup is invariably a cyclic structure having 4n+2 “delocalized”electrons where “n” is an integer equal to 1 or greater, as illustratedby phenyl groups (n=1), thienyl groups (n=1), furanyl groups (n=1),naphthyl groups (n=2), azulenyl groups (n=2), anthraceneyl groups (n=3)and the like. The aromatic radical may also include nonaromaticcomponents. For example, a benzyl group is an aromatic radical whichcomprises a phenyl ring (the aromatic group) and a methylene group (thenonaromatic component). Similarly, a tetrahydronaphthyl radical is anaromatic radical comprising an aromatic group (C₆H₃) fused to anonaromatic component —(CH₂)₄—. For convenience, the term “aromaticradical” is defined herein to encompass a wide range of functionalgroups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkylgroups, haloaromatic groups, conjugated dienyl groups, alcohol groups,ether groups, aldehyde groups, ketone groups, carboxylic acid groups,acyl groups (for example carboxylic acid derivatives such as esters andamides), amine groups, nitro groups, and the like. For example, the4-methylphenyl radical is a C₇ aromatic radical comprising a methylgroup, the methyl group being a functional group which is an alkylgroup. Similarly, the 2-nitrophenyl group is a C₆ aromatic radicalcomprising a nitro group, the nitro group being a functional group.Aromatic radicals include halogenated aromatic radicals such as4-trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phen-1-yloxy)(i.e., —OPhC(CF₃)₂PhO—), 4-chloromethylphen-1-yl,3-trifluorovinyl-2-thienyl, 3-trichloromethylphen-1-yl (i.e.,3-CCl₃Ph-), 4-(3-bromoprop-1-yl)phen-1-yl (i.e., 4-BrCH₂CH₂CH₂Ph-), andthe like. Further examples of aromatic radicals include4-allyloxyphen-1-oxy, 4-aminophen-1-yl (i.e., 4-H₂NPh-),3-amino-carbonylphen-1-yl (i.e., NH₂COPh-), 4-benzoylphen-1-yl,dicyanomethylidenebis(4-phen-1-yloxy) (i.e., —OPhC(CN)₂PhO—),3-methylphen-1-yl, methylenebis(4-phen-1-yloxy) (i.e., —OPhCH₂PhO—),2-ethylphen-1-yl, phenylethenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl,hexa-methylene-1,6-bis(4-phen-1-yloxy) (i.e., —OPh(CH₂)₆PhO—),4-hydroxymethylphen-1-yl (i.e., 4-HOCH₂Ph-), 4-mercaptomethylphen-1-yl(i.e., 4-HSCH₂Ph-), 4-methylthiophen-1-yl (i.e., 4-CH₃SPh-),3-methoxyphen-1-yl, 2-methoxycarbonylphen-1-yloxy (e.g., methylsalicyl), 2-nitro-methylphen-1-yl (i.e., 2-NO₂CH₂Ph),3-trimethylsilylphen-1-yl, 4-t-butyldimethylsilylphen-1-yl,4-vinylphen-1-yl, vinylidenebis(phenyl), and the like. The term “aC₃-C₁₀ aromatic radical” includes aromatic radicals containing at leastthree but no more than 10 carbon atoms. The aromatic radical1-imidazolyl (C₃H₂N₂—) represents a C₃ aromatic radical. The benzylradical (C₇H₇—) represents a C₇ aromatic radical.

As used herein the term “cycloaliphatic radical” refers to a radicalhaving a valence of at least one, and comprising an array of atoms whichis cyclic but which is not aromatic. As defined herein a “cycloaliphaticradical” does not contain an aromatic group. A “cycloaliphatic radical”may comprise one or more noncyclic components. For example, acyclohexylmethyl group (C₆H₁₁CH₂—) is a cycloaliphatic radical whichcomprises a cyclohexyl ring (the array of atoms which is cyclic butwhich is not aromatic) and a methylene group (the noncyclic component).The cycloaliphatic radical may include heteroatoms or may be composedexclusively of carbon and hydrogen. For convenience, the term“cycloaliphatic radical” is defined herein to encompass a wide range offunctional groups such as alkyl groups, alkenyl groups, alkynyl groups,haloalkyl groups, conjugated dienyl groups, alcohol groups, ethergroups, aldehyde groups, ketone groups, carboxylic acid groups, acylgroups (for example carboxylic acid derivatives such as esters andamides), amine groups, nitro groups, and the like. For example, the4-methylcyclopent-1-yl radical is a C₆ cycloaliphatic radical comprisinga methyl group, the methyl group being a functional group which is analkyl group. Similarly, the 2-nitrocyclobut-1-yl radical is a C₄cycloaliphatic radical comprising a nitro group, the nitro group being afunctional group. A cycloaliphatic radical may comprise one or morehalogen atoms which may be the same or different. Halogen atoms include,for example; fluorine, chlorine, bromine, and iodine. Cycloaliphaticradicals comprising one or more halogen atoms include2-trifluoromethylcyclohex-1-yl, 4-bromodifluoromethyIcyclooct-1-yl,2-chlorodifluoromethylcyclohex-1-yl, hexafluoroisopropylidene-2,2-bis(cyclohex-4-yl) (i.e., —C₆H₁₀C(CF₃)₂C₆H₁₀—),2-chloromethylcyclohex-1-yl, 3-difluoromethylenecyclohex-1-yl,4-trichloromethylcyclohex-1-yloxy,4-bromodichloromethyl-cyclohex-1-ylthio, 2-bromoethylcyclopent-1-yl,2-bromopropylcyclohex-1-yloxy (e.g., CH₃CHBrCH₂C₆H₁₀O—), and the like.Further examples of cycloaliphatic radicals include4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (i.e., H₂NC₆H₁₀—),4-aminocarbonylcyclopent-1-yl (i.e., NH₂COC₅H₈—),4-acetyloxycyclohex-1-yl, 2,2-dicyanoisopropylidenebis(cyclohex-4-yloxy)(i.e., —OC₆H₁₀C(CN)₂C₆H₁₀O—), 3-methylcyclohex-1-yl,methylenebis(cyclohex-4-yloxy) (i.e., —OC₆H₁₀CH₂C₆H₁₀O—),1-ethylcyclobut-1-yl, cyclopropylethenyl, 3-formyl-2-terahydrofuranyl,2-hexyl-5-tetrahydrofuranyl, hexamethylene-1,6-bis(cyclohex-4-yloxy)(i.e., —OC₆H₁₀(CH₂)₆C₆H₁₀O—), 4-hydroxymethylcyclohex-1-yl (i.e.,4-HOCH₂C₆H₁₀—), 4-mercapto-methylcyclohex-1-yl (i.e., 4-HSCH₂C₆H₁₀—),4-methylthiocyclohex-1-yl (i.e., 4-CH₃SC₆H₁₀—), 4-methoxycyclohex-1-yl,2-methoxycarbonylcyclohex-1-yloxy (2-CH₃OCOC₆H₁₀O—),4-nitro-methylcyclohex-1-yl (i.e., NO₂CH₂C₆H₁₀—),3-trimethylsilylcyclohex-1-yl, 2-t-butyldimethyl-silylcyclopent-1-yl,4-trimethoxysilylethylcyclohex-1-yl (e.g., (CH₃O)₃SiCH₂CH₂C₆H₁₀—),4-vinylcyclohexen-1-yl, vinylidenebis(cyclohexyl), and the like. Theterm “a C₃-C₁₀ cycloaliphatic radical” includes cycloaliphatic radicalscontaining at least three but no more than 10 carbon atoms. Thecycloaliphatic radical 2-tetrahydrofuranyl (C₄H₇O—) represents a C₄cycloaliphatic radical. The cyclohexylmethyl radical (C₆H₁₁CH₂—)represents a C₇ cycloaliphatic radical.

As used herein the term “aliphatic radical” refers to an organic radicalhaving a valence of at least one consisting of a linear or branchedarray of atoms which is not cyclic. Aliphatic radicals are defined tocomprise at least one carbon atom. The array of atoms comprising thealiphatic radical may include heteroatoms or may be composed exclusivelyof carbon and hydrogen. For convenience, the term “aliphatic radical” isdefined herein to encompass, as part of the “linear or branched array ofatoms which is not cyclic” a wide range of functional groups such asalkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups,conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups,ketone groups, carboxylic acid groups, acyl groups (for examplecarboxylic acid derivatives such as esters and amides), amine groups,nitro groups, and the like. For example, the 4-methylpent-1-yl radicalis a C₆ aliphatic radical comprising a methyl group, the methyl groupbeing a functional group which is an alkyl group. Similarly, the4-nitrobut-1-yl group is a C₄ aliphatic radical comprising a nitrogroup, the nitro group being a functional group. An aliphatic radicalmay be a haloalkyl group which comprises one or more halogen atoms whichmay be the same or different. Halogen atoms include, for example;fluorine, chlorine, bromine, and iodine. Aliphatic radicals comprisingone or more halogen atoms include the alkyl halides trifluoromethyl,bromodifluoromethyl, chlorodifluoromethyl, hexafluoroisopropylidene,chloromethyl, difluorovinylidene, trichloromethyl, bromodichloro-methyl,bromoethyl, 2-bromotrimethylene (e.g., —CH₂CHBrCH₂—), and the like.Further examples of aliphatic radicals include allyl, aminocarbonyl(i.e., —CONH₂), carbonyl, 2,2-dicyanoiso-propylidene (i.e.,—CH₂C(CN)₂CH₂—), methyl (i.e., —CH₃), methylene (i.e., —CH₂—), ethyl,ethylene, formyl (i.e., —CHO), hexyl, hexamethylene, hydroxymethyl(i.e., —CH₂OH), mercaptomethyl (i.e., —CH₂SH), methylthio (i.e., —SCH₃),methyithiomethyl (i.e., —CH₂SCH₃), methoxy, methoxy-carbonyl (i.e.,CH₃OCO—), nitromethyl (i.e., —CH₂NO₂), thiocarbonyl, trimethylsilyl(i.e., (CH₃)₃Si—), t-butyldimethylsilyl, 3-trimethyoxysilylpropyl (i.e.,(CH₃O)₃SiCH₂CH₂CH₂₋), vinyl, vinylidene, and the like. By way of furtherexample, a C₁-C₁₀ aliphatic radical contains at least one but no morethan 10 carbon atoms. A methyl group (i.e., CH₃—) is an example of a C₁aliphatic radical. A decyl group (i.e., CH₃(CH₂)₉—) is an example of aC₁₀ aliphatic radical.

As used herein, the term hydrocarbyl ether linkage refers to an oxygenatom linking a hydrocarbyl group to another hydrocarbyl group, anaromatic radical, a cycloaliphatic radical, or an aliphatic radical. Asused herein, the term aromatic ether linkage refers to an oxygen atomlinking an aromatic radical to another aromatic radical, acycloaliphatic radical, or an aliphatic radical. As used herein, theterm cycloaliphatic ether linkage refers to an oxygen atom linking acycloaliphatic radical to another cycloaliphatic radical, or analiphatic radical. As used herein, the term aliphatic ether linkagerefers to an oxygen atom linking an aliphatic radical to anotheraliphatic radical. As used herein, the term aromatic peripheral grouprefers to a peripheral group comprising at least one aromatic radical.As used herein, the term cycloaliphatic peripheral group refers to aperipheral group comprising at least one cycloaliphatic radical and notcomprising an aromatic radical. As used herein, the term aliphaticperipheral group refers to a peripheral group comprising at least onealiphatic radical and not comprising an aromatic radical or acycloaliphatic radical. As used herein, the term aliphatic polyol refersto a polyol comprising at least one aliphatic radical and not comprisinga cycloaliphatic radical or an aromatic radical. As used herein, theterm cycloaliphatic polyol refers to a polyol comprising at least onecycloaliphatic radical and not comprising an aromatic radical. As usedherein, the term aromatic polyol refers to a polyol comprising at leastone aromatic radical. As used herein the term SMC refers to Sheet MoldedCompounds and associated molding methods. As used herein the term BMCrefers to Bulk Molded Compounds and associated molding methods. As usedherein residue means the remainder of a compound utilized to form areaction product remaining in the reaction product wherein the residueis covalently bonded into the formed reaction product. As used hereinmethylene ether means a linking oxygen atom comprised within an alkylenechain. As used herein amino ether means a linking nitrogen atomcomprised within an alkylene chain.

The oligomeric polyol compositions disclosed herein comprise one or moreoligomeric polyols constituted by an oligomeric network linked to groupsat the periphery of the oligomeric network, referred to herein asperipheral groups. Although the precise structures of the oligomericpolyols have not been entirely elucidated, it is believed that theoligomeric network portion of the oligomeric polyol is comprised ofresidues of one or more polyols and residues of one or morepolyhydroxylated aromatic compounds, such as aromatic bisphenols. Theperipheral groups are constituted by either or both of a residue of apolyol and a residue of polyhydroxylated aromatic compounds, such as anaromatic bisphenol. A peripheral group is the residue of either apolyhydroxylated aromatic compound, such as an aromatic bisphenol or apolyol when either such residue is attached to the oligomeric network byone or more linking units, or a single linking unit.

The peripheral group may comprise a polyol residue directly linked to aresidue of a polyhydroxylated aromatic compound, such as an aromaticbisphenol, residue linked by a single linking unit to the oligomericnetwork, the combination of the polyol residue and the residue of thepolyhydroxylated aromatic compound, such as an aromatic bisphenol,residue, is considered as a peripheral group. A peripheral group is agroup containing one or more hydroxyl groups disposed in a location onthe oligomeric polyol such that one or more of the hydroxyl groups areavailable for reaction with a compound reactive with hydroxyl groups. Inthis context, the groups reactive with a hydroxyl group may beisocyanate groups, isocyanurate groups, carbamate ester groups, epoxygroups, carbonate groups or the like. The groups reactive with ahydroxyl group may be isocyanate groups. The peripheral groups may bethe outermost units of the oligomeric polyol. The peripheral groups maycontain but a single residue of a polyol or a single residue of apolyhydroxylated aromatic compound, such as an aromatic bisphenol.

The oligomeric network comprises residues of at least onepolyhydroxylated aromatic compound, such as an aromatic bisphenol, andresidues of at least one polyol having at least three hydroxyl groups.This means that a free polyol to which the polyol residue relates hasthree or more free hydroxyl groups. Such polyols may be consideredmonomeric in the sense that they are not themselves polymers. Thepolyols may have molecular weights under 1000 grams per mole, under 500grams per mole, or under 300 grams per mole. The polyols may havemolecular weights of 100 grams per mole or greater or 130 grams per moleor greater. The polyols may be employed as mixtures of structurallyrelated polyols having different molecular weights, and such mixturesqualify as polyols as defined herein when the molecular weights of fiftymole percent of the constituent polyols meet the defined molecularweights. A single oligomeric polyol may comprise the residues of one ormore different polyols. For example, an oligomeric polyol may containresidues of two different polyols having differing chemical and physicalproperties. For example, the residues of a first constituent polyol maycomprise one or more oxygen ether groups, one or more amino ethergroups, or both one or more oxygen ether groups and one or more aminoether groups, while a second constituent monomeric polyol residue maycomprise one or more oxygen ether groups but be substantially free ofamino ether groups.

A variety linking unit types within the oligomeric network are possible.Any linking unit that can bind the constituent residues of theoligomeric network to one another may be used. The linking unit may be aheteroatom containing moiety capable of bonding two hydrocarbyl moietiestogether. Exemplary linking units may be oxygen atoms of hydrocarbylether linkages, carbonate groups, carbonyl groups, ester groups,thioether sulfur atoms, acetal groups, thioacetal groups, acylal groups,orthoester groups, orthocarbonate groups, silicon containing groups, andamino ether moieties. The linking unit may be an ether, amino ether orcarbonate moiety. The linking unit may be a carbonate moiety. Thepolyhydroxylated aromatic compound residues may form two bonds to otheroligomeric network residues but may form additional bonds to othernetwork residues. For example, the residue may be that ofpolyhydroxylated aromatic compound having three or more hydroxyl groups,for example one or more branching agents commonly utilized in preparingpolycarbonate resins for example the residues of1,1,1-tris(4-hydoxyphenyl)ethane and2,6-bis[(2-hydoxy-3,5-dimethyl)methyl]-4-methylphenol (CAS. No.35924-04-0). In such cases, the residues of the polyhydroxylatedaromatic compound having three or more hydroxyl groups may be linked tomore than two other residues within the oligomeric network.

The oligomeric network comprises residues of polyols linked to two ormore other network residues which may be residues of a polyhydroxylatedaromatic compound, residues of another polyol, or a combination of oneor more residues of a polyhydroxylated aromatic compound and residues ofone or more other polyols. A polyol residue within the oligomericnetwork may in some instances be linked to one or more other residueswithin the oligomeric network and also to one or more peripheral groups.The oligomeric network may comprise a plurality of hydroxyl groupspendant from one or more network constituent residues. In someinstances, fifty mole percent, seventy-five mole percent, ninety-fivemole percent, or ninety-nine mole percent of polyol residues within theoligomeric network comprise one or more pendant hydroxyl groups.

The oligomeric polyols comprise a plurality of peripheral groups boundto the oligomeric network by a plurality of linking units. Eachperipheral group is bound to the oligomeric network by at least a singlelinking unit. The nature of the linking units may depend on the mannerin which the oligomeric polyol is prepared. Any linking unit that canbind the peripheral group to the oligomeric network may be used. Thelinking unit binding the peripheral group to the oligomeric network maybe a heteroatom containing moiety capable of bonding two hydrocarbylmoieties together. Exemplary linking units may be oxygen atoms ofhydrocarbyl ether linkages, carbonate groups, carbonyl groups, estergroups, thioether sulfur atoms, acetal groups, thioacetal groups, acylalgroups, orthoester groups, orthocarbonate groups, silicon containinggroups, and amino ether moieties. The linking unit may be an ether,amino ether or carbonate moiety. The linking unit may be a carbonatemoiety. Thus, the linking unit binding a peripheral group to theoligomeric network may be a single atom linking unit such as the oxygenatom of an ether group or the sulfur atom of a thioether group; or amulti-atom linking unit such as carbonate groups and ester groups. Theperipheral groups comprise one or more pendant hydroxyl groups. Apendant hydroxyl group is located on the structure of the oligomericnetwork in a location wherein it is available to react with compoundsthat are reactive with hydroxyl groups.

Disclosed herein is an oligomeric polyol composition comprising anoligomeric polyol comprising an oligomeric network and one or moreperipheral groups which are hydrocarbyl groups comprising at least onependant hydroxyl group. The hydrocarbyl groups may be bound to theoligomeric network by a plurality of linking units such are disclosedherein. The hydrocarbyl groups may be aromatic radicals, cycloaliphaticradicals, aliphatic radicals or a combination of such radicals. In oneor more instances, at least a portion of the linking units are oxygenatoms of hydrocarbyl ether linkages which may constitute oxygen atoms ofaromatic ether linkages, oxygen atoms of cycloaliphatic ether linkages,or oxygen atoms of aliphatic ether linkages.

Disclosed herein is an oligomeric polyol composition comprising anoligomeric polyol comprising an oligomeric network and one or moreperipheral groups, wherein at least a portion of the peripheral groupsare (i) aliphatic peripheral groups comprising a residue of at least onemonomeric aliphatic polyol having at least two pendant hydroxyl groups;(ii) cycloaliphatic peripheral groups comprising a residue of at leastone monomeric cycloaliphatic polyol having at least two pendant hydroxylgroups; (iii) aromatic peripheral groups comprising a residue of atleast one monomeric aromatic polyol having at least two pendant hydroxylgroups; (iv) aromatic peripheral groups comprising a residue of at leastone polyhydroxylated aromatic compound having at least one pendanthydroxyl group; (v) an adduct comprising at least one polyhydroxylatedaromatic compound residue and at least one residue of an aliphaticpolyol having at least two pendant hydroxyl groups; (vi) an adductcomprising at least one polyhydroxylated aromatic compound residue andat least one residue of a cycloaliphatic polyol having at least twopendant hydroxyl groups; or (vii) an adduct comprising at least onepolyhydroxylated aromatic compound residue and at least one or moreresidue of a monomeric aromatic polyol having at least two pendanthydroxyl groups.

As disclosed herein, the oligomeric polyol may comprise residues of apolyol as constituents of either or both of the oligomeric network andthe peripheral groups, wherein the polyol residue and the polyol towhich it relates comprise at least one methylene ether group. The polyolresidue and the polyol to which it relates, may comprise primaryhydroxyl groups, secondary hydroxyl groups, or a mixture of primary andsecondary hydroxyl groups. The polyol residue and the monomeric polyolto which it relates, may comprise secondary hydroxyl groups and besubstantially free of primary and tertiary hydroxyl groups. In someinstances, the polyol residue and the polyol to which it relates, maycomprise tertiary hydroxyl groups in addition to primary and/orsecondary hydroxyl groups. Substantially free of primary and tertiaryhydroxyl groups means that such hydroxyls groups comprise less thanabout 1 percent by weight of the described compositions, or less thanabout 0.5 percent by weight of the described compositions.

Disclosed herein is an oligomeric polyol composition comprising anoligomeric polyol comprising an oligomeric network and one or moreperipheral groups, wherein either or both of the oligomeric network andthe peripheral groups comprises residues of at least one polyol which isa polyhydroxylated amine. The polyhydroxylated amine residue and thepolyhydroxylated amine to which it relates comprise secondary hydroxylgroups or residues thereof, and may be substantially free of primary andtertiary hydroxyl groups or residues thereof.

The peripheral groups may be represented by (a) structure I

wherein R¹ and R² are independently at each occurrence a hydrogen atom,or a hydrocarbyl group such that R¹ and R², either alone or together,comprise at least two hydroxyl groups wherein R¹ and/or R² optionallycontain an internal functional group containing a heteroatom; R³ isindependently at each occurrence a non-carbon substituent or ahydrocarbyl group; W is a bond or a linking group; the variables n andn′ are independently an integer from 0 to 4; and X¹ is a linking unitjoining peripheral group I, II or III to oligomeric network Y¹,oligomeric network Y¹ comprising residues of at least one aromaticbisphenol and residues of at least one monomeric polyol having at leastthree hydroxyl groups.

The oligomeric networks Y¹ and linking units X¹ are not constituents ofperipheral groups I, II and III, but are shown to illustrate therelationship within an oligomeric polyol between the peripheral groups,the linking unit and the oligomeric network.

Disclosed herein is an oligomeric polyol composition comprising anoligomeric polyol comprising an oligomeric network and one or moreperipheral groups, wherein at least a portion of the peripheral groupscomprise a residue of a polyol and have structure I

wherein R¹ and R² are independently at each occurrence a hydrogen atom,a C₁-C₃₀ aliphatic radical, a C₅-C₃₀ cycloaliphatic radical, or a C₆-C₃₀aromatic radical, or R¹ and R² may together form a C₅-C₃₀ cycloaliphaticradical or a C₆-C₃₀ aromatic radical; with the proviso that R¹ and R²,either alone or together, comprise at least two hydroxyl groups, whereinR¹ and/or R² optionally contain an internal functional group containinga heteroatom; and X¹ is a linking unit joining peripheral group I tooligomeric network Y¹, oligomeric network Y¹ comprising residues of atleast one aromatic bisphenol and residues of at least one monomericpolyol having at least three hydroxyl groups.

Additionally, R¹ and R² are independently at each occurrence a hydrogenatom, a C₁-C₂₅ aliphatic radical, a C₅-C₂₅ cycloaliphatic radical, or aC₆-C₂₅ aromatic radical, or R¹ and R² may together form a C₅-C₃₀cycloaliphatic radical or a C₆-C₃₀ aromatic radical; with the provisothat R¹ and R², either alone or together, comprise at least two hydroxylgroups, wherein R¹ and/or R² optionally contain an internal functionalgroup containing a heteroatom; and X¹ is a linking unit joiningperipheral group I to oligomeric network Y¹, oligomeric network Y¹comprising residues of at least one aromatic bisphenol and residues ofat least one monomeric polyol having at least three hydroxyl groups.

Further, R¹ and R² are independently at each occurrence a hydrogen atom,a C₁-C₁₉ aliphatic radical, a C₅-C₁₉ cycloaliphatic radical, or a C₆-C₂₂aromatic radical; with the proviso that R¹ and R², either alone ortogether, comprise at least two hydroxyl groups, wherein R¹ and/or R²optionally contain an internal functional group containing a heteroatomwhich is an oxygen atom, a sulfur atom or a nitrogen atom; and X¹ is alinking unit joining peripheral group I to oligomeric network Y¹,oligomeric network Y¹ comprising residues of at least one aromaticbisphenol and residues of at least one monomeric polyol having at leastthree hydroxyl groups.

Specific examples of peripheral groups having structure I are given inTable 1.

TABLE 1 IIlustrative Peripheral Groups I Entry Structure X¹ R¹ R² Ia

O CH₃ See Structure Ib

OCOO CH₃ See Structure Ic

OCOO CH₃ See Structure Id

OCOO See structure H Ie

O See Structure CH₃ If

OCOO CH₃ See structure Ig

O CH₃ See structure Ih

O See structure Et Ii

OCOO See structure Et Ij

O See structure Et Ik

OCOO See structure CH₃ Il

OCOO See structure CH₃ Im

O See structure CH₃ In

OCOO CH₃ See structure Io

O CH₃ See Structure Ip

OCOO CH₃ See structure Iq

O CH₃ See Structure Ir

OCOO H See Structure

Illustrative peripheral groups I represent aliphatic peripheral groups,Entries Ia-Ih, II-Im and Ir; cycloaliphatic peripheral groups, EntriesIi-Ij, In, and Io-Iq; and aromatic peripheral groups, Entry Ik, bound toan oligomeric network Y¹ by a linking unit X¹ which is an oxygen ethersingle atom linking unit, or a multi-atom linking unit which is acarbonate linking unit.

Disclosed herein is an oligomeric polyol composition comprising anoligomeric polyol comprising an oligomeric network and one or moreperipheral groups, wherein at least a portion of the peripheral groupscomprise a residue of an aromatic bisphenol and have structure II

wherein R³ is independently at each occurrence a halogen atom, a nitrogroup, a C₁-C₁₀ aliphatic radical, a C₅-C₁₀ cycloaliphatic radical, or aC₆-C₂₀ aromatic radical; W is a bond or a linking oxygen atom, a sulfuratom, a sulfur oxide linking group, a C₁-C₁₀ aliphatic radical, a C₅-C₁₀cycloaliphatic radical, or a C₆-C₂₀ aromatic radical; the variables nand n′ are independently an integer from 0 to 4; and X¹ is a linkingunit joining peripheral group II to oligomeric network Y¹, oligomericnetwork Y¹ comprising residues of at least one aromatic bisphenol andresidues of at least one monomeric polyol having at least three hydroxylgroups.

Additionally, R³ is independently at each occurrence a halogen atom, anitro group, a C₁-C₅ aliphatic radical, a C₅-C₁₀ cycloaliphatic radical,or a C₆-C₁₀ aromatic radical; W is a bond or a linking oxygen atom, asulfur atom, a sulfur oxide linking group, a C₁-C₅ aliphatic radical, aC₅-C₁₀ cycloaliphatic radical, or a C₆-C₁₅ aromatic radical; thevariables n and n′ are independently an integer from 0 to 4; and X¹ is alinking unit joining peripheral group II to oligomeric network Y¹,oligomeric network Y¹ comprising residues of at least one aromaticbisphenol and residues of at least one monomeric polyol having at leastthree hydroxyl groups.

Further, R³ is independently at each occurrence a halogen atom, a C₁-C₂aliphatic radical, a C₅-C₈ cycloaliphatic radical, or a C₆-C₁₀ aromaticradical; W is a bond or a linking oxygen atom, a sulfur atom, a sulfuroxide linking group, a C₁-C₃ aliphatic radical, a C₅-C₉ cycloaliphaticradical, or a C₆-C₁₃ aromatic radical; the variables n and n′ areindependently an integer from 0 to 2; and X¹ is a linking unit joiningperipheral group II to oligomeric network Y¹, oligomeric network Y¹comprising residues of at least one aromatic bisphenol and residues ofat least one monomeric polyol having at least three hydroxyl groups.

Specific examples of peripheral groups falling within generic structureII are given in Table 2.

TABLE 2 IIlustrative Peripheral Groups II Entry Structure X¹ R³ R³ n′ nIIa

O — — 0 0 IIb

O CH₃ CH₃ 1 1 IIc

O — — 0 0 IId

O Cl Cl 2 2 IIe

OCOO Br Br 1 1 IIf

OCOO — — 0 0 IIg

OCOO — — 0 0 IIh

OCOO — — 0 0 IIi

OCOO 2 2 Br Br IIj

O — — 0 0 IIk

O Et Et 1 1 IIl

O Ph Ph 1 1 IIm

O — — 0 0 IIn

O — — 0 0 IIo

OCOO — — 0 0 IIp

O — — 0 0 IIq

O CH₃ CH₃ 2 2 IIr

OCOO CH₃ CH₃ 2 2 IIs

O

— 1 0 IIt

OCOO

1 1 IIu

OCOO CH₃

1 1 IIv

OCOO Br Cl 1 1

Illustrative peripheral groups IIa-IIv represent aromatic peripheralgroups comprised of residues of an aromatic bisphenol and comprising oneor more pendant hydroxy groups. Peripheral groups II are bound to anoligomeric network Y¹ of the oligomeric polyol by a linking unit whichis an oxygen ether single atom linking unit, Entries IIa-IId, IIj-IIn,IIp-IIq and IIs (oxygen), or a multi-atom linking unit which is acarbonate linking unit, Entries IIe-IIh, IIo, IIr and IIu-IIv.

Disclosed herein is an oligomeric polyol composition comprising anoligomeric polyol comprising an oligomeric network and one or moreperipheral groups, wherein at least a portion of the peripheral groupscomprise a residue of a monomeric polyol linked through a residue of anaromatic bisphenol and a linking unit to the oligomeric network, andhave structure III

wherein R¹ and R² are independently at each occurrence a hydrogen atom,a C₁-C₃₀ aliphatic radical, a C₅-C₃₀ cycloaliphatic radical, a C₆-C₃₀aromatic radical, or R¹ and R² may together form a C₅-C₃₀ cycloaliphaticradical or a C₆-C₃₀ aromatic radical; with the proviso that R¹ and R²,either alone or together, comprise at least two hydroxyl groups, whereinR¹ and/or R² optionally contain an internal functional group containinga heteroatom; R³ is independently at each occurrence a halogen atom, anitro group, a C₁-C₁₀ aliphatic radical, a C₅-C₁₀ cycloaliphaticradical, or a C₆-C₂₀ aromatic radical; W is a bond or a linking oxygenatom, a sulfur atom, a sulfur oxide linking group, a C₁-C₁₀ aliphaticradical, a C₅-C₁₀ cycloaliphatic radical, or a C₆-C₂₀ aromatic radical;the variables n and n′ are independently an integer from 0 to 4; and X¹is a linking unit joining peripheral group III to oligomeric network Y¹,oligomeric network Y¹ comprising residues of at least one aromaticbisphenol and residues of at least one monomeric polyol having at leastthree hydroxyl groups.

Additionally, R¹ and R² are independently at each occurrence a hydrogenatom, a C₁-C₂₅ aliphatic radical, a C₅-C₂₅ cycloaliphatic radical, or aC₆-C₂₅ aromatic radical, or R¹ and R² may together form a C₅-C₃₀cycloaliphatic radical or a C₆-C₃₀ aromatic radical; with the provisothat R¹ and R², either alone or together, comprise at least two hydroxylgroups, wherein R¹ and/or R² optionally contain an internal functionalgroup containing a heteroatom; R³ is independently at each occurrence ahalogen atom, a nitro group, a C₁-C₅ aliphatic radical, a C₅-C₁₀cycloaliphatic radical, or a C₆-C₁₀ aromatic radical; W is a bond or alinking oxygen atom, a sulfur atom, a sulfur oxide linking group, aC₁-C₅ aliphatic radical, a C₅-C₁₀ cycloaliphatic radical, or a C₆-C₁₅aromatic radical; the variables n and n′ are independently an integerfrom 0 to 4; and X¹ is a linking unit joining peripheral group III tooligomeric network Y¹, oligomeric network Y¹ comprising residues of atleast one aromatic bisphenol and residues of at least one monomericpolyol having at least three hydroxyl groups.

Further, R¹ and R² are independently at each occurrence a hydrogen atom,a C₁-C₁₉ aliphatic radical, a C₅-C₁₉ cycloaliphatic radical, or a C₆-C₂₂aromatic radical; with the proviso that R¹ and R², either alone ortogether, comprise at least two hydroxyl groups, wherein R¹ and/or R²optionally contain an internal functional group containing a heteroatomwhich is an oxygen atom, a sulfur atom or a nitrogen atom; R³ isindependently at each occurrence a halogen atom, a C₁-C₂ aliphaticradical, a C₅-C₈ cycloaliphatic radical, or a C₆-C₁₀ aromatic radical; Wis a bond or a linking oxygen atom, a sulfur atom, a sulfur oxidelinking group, a C₁-C₃ aliphatic radical, a C₅-C₉ cycloaliphaticradical, or a C₆-C₁₃ aromatic radical; the variables n and n′ areindependently an integer from 0 to 2; and X¹ is a linking unit joiningperipheral group III to oligomeric network Y¹, oligomeric network Y¹comprising residues of at least one aromatic bisphenol and residues ofat least one monomeric polyol having at least three hydroxyl groups.

TABLE 3 Illustrative Peripheral Groups III Entry Structure X¹ R³ R³ n′ nIIla

O — — 0 0 IIIb

O CH₃ CH₃ 1 1 IIIc

O — — 0 0 IIId

O Cl Cl 2 2 IIIe

O Br Br 1 1 IIIf

O — — 0 0 IIIg

O — — 0 0 IIIh

IIIi

O — — 0 0 IIIj

O Et Et 1 1 IIIl

IIIm

OCO — — 0 0 IIIn

OCO — — 0 0 IIIo

O — — 0 0

Illustrative peripheral groups III represent aromatic peripheral groupsand are comprised of residues of an aromatic bisphenol and a monomericpolyol and may be referred to herein as an adduct comprising at leastone aromatic bisphenol residue and at least one residue of a monomericaromatic polyol. The illustrated peripheral groups comprise a residue ofthe monomeric polyol bound through the residue of the aromatic bisphenoland a linking unit X¹ to an oligomeric network Y¹ and comprise two ormore pendant hydroxy groups. Peripheral groups III are bound to anoligomeric network Y¹ of the oligomeric polyol by a linking unit whichX¹ is an oxygen ether or a carbonate group. In the illustratedperipheral groups IIIa-IIIo the residue of the outermost monomericpolyol residue is bound by an oxygen atom to the aromatic bisphenolresidue. In an alternate set of illustrative examples (not shown), theresidue of the outermost monomeric polyol residue is bound by acarbonate group to the aromatic bisphenol residue.

Disclosed herein is an oligomeric polyol composition comprising anoligomeric polyol comprising an oligomeric network and one or moreperipheral groups, wherein the oligomeric network and at least a portionof the peripheral groups comprise a residue of a polyhydroxylatedaromatic compound, such as an aromatic bisphenol. Polyhydroxylatedaromatic compounds to which such residues relate include compounds whichcorrespond to the formula Ar—(OH)_(f) wherein Ar comprises an aromaticmoiety as disclosed herein and f is an integer of about 2 to about 6, or2 to 4. The polyhydroxylated aromatic compounds may be diphenols.Exemplary diphenols include hydroquinone, resorcinol,dihydroxybiphenyls, bis(hydroxyphenyl)-C1-C5 alkanes,bis-(hydroxy-phenyl)-C5-C6 cycloalkanes, bis(hydroxyphenyl)ethers,bis(hydroxyphenyl)sulfoxides, bis(hydroxy phenyl) ketones,bis(hydroxyphenyl)sulfones and 4,4″-bis(hydroxyphenyl)diisopropylbenzenes, as well as derivatives thereof which have brominated and/orchlorinated nuclei. Exemplary diphenols may be 4,4′-dihydroxybiphenyl,bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane,1,1-bis(4-hydroxyphenyl)-cyclohexane,1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,4,4-dihydroxydiphenyl sulfide and 4,4-dihydroxydiphenyl sulfone, as wellas di- and tetrabrominated or chlorinated derivatives thereof, such as2,2-bis(3-chloro-4-hydroxyphenyl) propane,2,2-bis-(3,5-dichloro-4-hydroxyphenyl)propane or2,2-bis(3,5-dibromo-4-hydroxy-phenyl)propane. The diphenols can be usedindividually or as arbitrary mixtures. The diphenols may be aromaticbisphenols to which such residues relate include aromatic bisphenolshaving structure IV

wherein R³ is independently at each occurrence a halogen atom, a nitrogroup, a C₁-C₁₀ aliphatic radical, a C₅-C₁₀ cycloaliphatic radical, or aC₆-C₂₀ aromatic radical; W is a bond or a linking oxygen atom, a sulfuratom, a sulfur oxide linking group, a C₁-C₁₀ aliphatic radical, a C₅-C₁₀cycloaliphatic radical, or a C₆-C₂₀ aromatic radical; and the variablesn and n′ are independently an integer from 0 to 4.

Additionally, R³ is independently at each occurrence a halogen atom, anitro group, a C₁-C₅ aliphatic radical, a C₅-C₁₀ cycloaliphatic radical,or a C₆-C₁₀ aromatic radical; W is a bond or a linking oxygen atom, asulfur atom, a sulfur oxide linking group, a C₁-C₅ aliphatic radical, aC₅-C₁₀ cycloaliphatic radical, or a C₆-C₁₅ aromatic radical; and thevariables n and n′ are independently an integer from 0 to 4.

Further, R³ is independently at each occurrence a halogen atom, a C₁-C₂aliphatic radical, a C₅-C₈ cycloaliphatic radical, or a C₆-C₁₀ aromaticradical; W is a bond or a linking oxygen atom, a sulfur atom, a sulfuroxide linking group, a C₁-C₃ aliphatic radical, a C₅-C₉ cycloaliphaticradical, or a C₆-C₁₃ aromatic radical; and the variables n and n′ areindependently an integer from 0 to 2.

TABLE 4 Illustrative Aromatic Bisphenols IV Entry Structure R³ R³ n′ nIVa

— — 0 0 IVb

CH₃ CH₃ 1 1 IVc

— — 0 0 IVd

Cl Cl 2 2 IVe

Br Br 1 1 IVf

— — 0 0 IVg

— — 0 0 IVh

Et — 1 0 IVi

Et Et 1 1 IVj

— — 0 0 IVk

— — 0 0 IVl

— — 0 0 IVm

— — 0 0 IVn

— — 0 0 IVo

— — 0 0 IVp

— — 0 0 IVq

CH₃ CH₃ 2 2 IVr

CH₃ CH₃ 2 2 IVs

— — 0 0 IVt

— — 0 0 IVu

— — 0 0 IVv

— — 0 0

Disclosed herein is an oligomeric polyol composition comprising anoligomeric polyol comprising an oligomeric network and one or moreperipheral groups, wherein the oligomeric network and at least a portionof the peripheral groups comprise residues of one or more polyols.Polyols to which such resides relate include polyols having structure V

wherein R¹ and R² are independently at each occurrence a hydrogen atom,a C₁-C₃₀ aliphatic radical, a C₅-C₃₀ cycloaliphatic radical, a C₆-C₃₀aromatic radical, or R¹ and R² may together form a C₅-C₃₀ cycloaliphaticradical or a C₆-C₃₀ aromatic radical; with the proviso that R¹ and R²,either alone or together, comprise at least two hydroxyl groups, whereinR¹ and/or R² optionally contain an internal functional group containinga heteroatom.

Additionally, R¹ and R² are independently at each occurrence a hydrogenatom, a C₁-C₂₅ aliphatic radical, a C₅-C₂₅ cycloaliphatic radical, or aC₆-C₂₅ aromatic radical, or R¹ and R² may together form a C₅-C₃₀cycloaliphatic radical or a C₆-C₃₀ aromatic radical; with the provisothat R¹ and R², either alone or together, comprise at least two hydroxylgroups, wherein R¹ and/or R² optionally contain an internal functionalgroup containing a heteroatom.

Further, R¹ and R² are independently at each occurrence a hydrogen atom,a C₁-C₁₉ aliphatic radical, a C₅-C₁₉ cycloaliphatic radical, or a C₆-C₂₂aromatic radical; with the proviso that R¹ and R², either alone ortogether, comprise at least two hydroxyl groups, wherein R¹ and/or R²optionally contain an internal functional group containing a heteroatomwhich is an oxygen atom, a sulfur atom or a nitrogen atom.

Specific examples of polyols V are given in Table 5.

TABLE 5 Illustrative Monomeric Polyols V Entry Structure R¹ R² Va

CH₃ See Structure Vb

CH₃ See Structure Vc

CH₃ See Structure Vd

See Structure H Ve

See Structure CH₃ Vf

CH₃ See Structure Vg

Et See Structure Vh

See Structure Et Vi

See Structure Et Vj

See Structure CH₃ Vk

See Structure CH₃ Vl

See Structure CH₃ Vm

See Structure Et Vn

CH₃ See Structure Vo

CH₃ See Structure Vp

Vq

Vr

Vs

Vt

CH₃ See Structure Vu

See Structure See Structure Vv

H See Structure Vw

See Structure H Vx

See Structure H

Illustrative polyols Va-Vv represent aliphatic polyols, Entries Va-Vh,VI-Vm and Vp-Vx; cycloaliphatic polyols, Entries Vi-Vj and Vn-Vo; andaromatic polyols, Entries Vh and Vk. Aliphatic polyols Vw and Vxrepresent ester polyols.

Exemplary chain terminators used in aromatic polycarbonates includephenolic compounds, exemplary phenolic compounds include phenol,p-chlorophenol, p-tert-butylphenol, 4-(1,3-dimethyl-butyl)-phenol and2,4,6-tribromophenol; long chain alkylphenols, such as monoalkylphenolsor dialkylphenols which contain a total of 8 to 20 C atoms in theiralkyl substituents, specific examples include 3,5-di-tert-butyl-phenol,p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol,2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol.Exemplary branching agents tri- or multi-functional phenols for examplephloroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene,4,4-dimethyl-2,4,6-tris(4-hydroxyphenyl) heptane,1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane,tris(4-hydroxyphenyl)-phenyl-methane,2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]-propane, 2,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]phenol,tetrakis(4-hydroxyphenyl)-methane,2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol,2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl) propane, ortetrakis(4-[1-(4-hydroxyphenyl)-1-methylethyl]-phenoxy)-methane.

The oligomeric polyol compositions comprising oligomeric polyols may beprepared by reacting a polyol or a suitable polyol derivative with apolyhydroxylated aromatic compound, such as an aromatic bisphenol or apolyhydroxylated aromatic compound derivative, such as an aromaticbisphenol derivative, under conditions promoting the formation of anoligomeric network comprising polyhydroxylated aromatic compoundresidues, such as aromatic bisphenol residues, and polyol residues, theoligomeric network being linked to a plurality of peripheral groupscomprising one or more hydroxyl groups. The reaction may advantageouslybe carried out in the presence of a catalyst or non-catalyst promoter.Illustrative catalysts and promoters include organic bases, inorganicbases, metal oxides, and organometallics. Catalysts are distinguishedfrom promoters in that promoters are consumed during the formation ofthe oligomeric polyol whereas catalysts are not consumed. Illustrativeorganic bases include salts of carboxylic acids such as sodium acetateand tri-octyl ammonium isovalerate; salts of sulfonic acids such assodium dodecyl sulfonate, amine bases, such as trialkyl aminesexemplified by tri-butyl amine, N,N′-tetra-isopropyl ethylene diamine,polyhydroxylated amines such as tris(hydroxypropyl)amine andamine-containing monomeric polyols such as Vf-Vm in Table 5 herein;amidine bases such as N,N′-tri-isopropyl phenyl amidine andN,N′-tri-methyl butyl amidine, and guanidine bases such asBarton-Elliott bases illustrated by N,N′,N″-penta-isopropyl guanidine.Illustrative inorganic bases include metal carbonates such as sodiumcarbonate, potassium carbonate, magnesium carbonate and bariumcarbonate; metal hydroxides such as lithium hydroxide, sodium hydroxide,potassium hydroxide and barium hydroxide; illustrative metal oxidesinclude aluminum oxide, silica, calcium oxide, magnesium oxide, tinoxide, and zinc oxide; and illustrative organometallics includetri-isopropyl aluminate, tetraalkyl zirconates, and organometallictransesterification catalysts such as tetra-isopropyl titanate andtetra-octyl titanate.

The formation of the oligomeric polyol may occur by activation of aprimary or secondary hydroxyl group of the polyol toward displacement byan oxygen atom of the polyhydroxylated aromatic compound, such as anaromatic bisphenol, residue. Such activation is conveniently achieved bycontacting the polyol at moderate temperatures, for example of about 50°C. or greater about 75° C. or greater, or about 100° C. or greater andfor example of about 250° C. or less, or about 225° C. or less, or about200° C. or less, with a polyhydroxylated aromatic compound, such as anaromatic bisphenol, residue containing one or more carbonate linkages inthe presence of a suitable catalyst or promoter. The activation of apolyol hydroxyl group can be effected, for example, by causing ahydroxyl group of the polyol to react with a carbonate linkage of anoligomeric or polymeric polyhydroxylated aromatic compound, aromaticbisphenol, polycarbonate in the presence of a catalyst or promoter suchas those disclosed herein to generate a mixed carbonate linkage betweenthe monomeric polyol and a polyhydroxylated aromatic compound, anaromatic bisphenol, residue. This mixed carbonate residue undergoes lossof carbon dioxide and formation of an aromatic ether linkage between aresidue of polyhydroxylated aromatic compound, an aromatic bisphenol,and a residue of a polyol. The mechanism by which the aromatic etherlinkage is formed may involve loss of carbon dioxide from the mixedcarbonate linkage and recombination of the reactive polyhydroxylatedaromatic compound, aromatic bisphenol, and monomeric components, or bydisplacement of the carbonate linkage by nucleophic attack by aphenolate species. In one such scenario, a nucleophic polyhydroxylatedaromatic compound, aromatic bisphenol, species is created as the mixedcarbonate linkage is formed. This nucleophic polyhydroxylated aromaticcompound, aromatic bisphenol, species in turn attacks the carbon atom ofthe polyol bearing the newly created mixed carbonate linkage and formsan ether linkage between the nucleophic polyhydroxylated aromaticcompound, aromatic bisphenol, species and the polyol residue. While notwishing to be bound by the theory just described, those of ordinaryskill in the art will appreciate its plausibility and that it accountsfor the results observed. The process is shown schematically in Scheme 1in which the nucleophilic bisphenol species is shown for illustrativepurposes as a phenolate species.

Alternatively, the oligomeric polyol may comprise as linking unitsbetween the polyol residues and residues of the polyhydroxylatedaromatic compound primarily carbonate units, or a mixture of carbonatelinking units and ether linking units.

As noted, the polycarbonate employed may be either an oligomericmaterial or may be a high molecular weight material. In one or moreaspects, a polycarbonate containing significant amounts of both high andlow molecular weight polycarbonate may be employed in the same reactionmixture in which the oligomeric polyol is formed. The polycarbonate mayhave a number average molecular weight of about 1000 grams/mole orgreater, about 10,000 grams/mole or greater or about 20,000 grams/moleor greater. The polycarbonate may have a number average molecular weightof about 100,000 or less, about 80,000 grams per mole or less, or about60,000 grams per mole or less.

The polycarbonate may be a copolycarbonate comprising two or moredifferent polyhydroxylated aromatic structural types. Alternatively, thepolycarbonate may a homopolymer comprising polyhydroxylated aromaticresidues of a single structural type, for example bisphenol A residues.The polycarbonate may comprise endcap groups provided by common chainterminators such as cumyl phenol end groups or phenol end groups.Alternately, the polycarbonate may comprise aromatic hydroxyl end groupsonly. The polycarbonate may be branched or linear and may be commercialgrade polycarbonate or be scrap polycarbonate recovered from apolycarbonate molding operation, to give just one example.

Polycarbonates suitable for use in accordance with one or more aspectsof this disclosure may be represented by generic structure VI

wherein R³ is independently at each occurrence a halogen atom, a nitrogroup, a C₁-C₁₀ aliphatic radical, a C₅-C₁₀ cycloaliphatic radical, or aC₆-C₂₀ aromatic radical; W is a bond or a linking oxygen atom, a sulfuratom, a sulfur oxide linking group, a C₁-C₁₀ aliphatic radical, a C₅-C₁₀cycloaliphatic radical, or a C₆-C₂₀ aromatic radical; and the variablesn and n′ are independently an integer from 0 to 4.

Additionally, R³ is independently at each occurrence a halogen atom, anitro group, a C₁-C₅ aliphatic radical, a C₅-C₁₀ cycloaliphatic radical,or a C₆-C₁₀ aromatic radical; W is a bond or a linking oxygen atom, asulfur atom, a sulfur oxide linking group, a C₁-C₅ aliphatic radical, aC₅-C₁₀ cycloaliphatic radical, or a C₆-C₁₅ aromatic radical; and thevariables n and n′ are independently an integer from 0 to 4.

Further, R³ is independently at each occurrence a halogen atom, a C₁-C₂aliphatic radical, a C₅-C₈ cycloaliphatic radical, or a C₆-C₁₀ aromaticradical; W is a bond or a linking oxygen atom, a sulfur atom, a sulfuroxide linking group, a C₁-C₃ aliphatic radical, a C₅-C₉ cycloaliphaticradical, or a C₆-C₁₃ aromatic radical; and the variables n and n′ areindependently an integer from 0 to 2.

Specific examples of suitable aromatic bisphenol polycarbonates aregiven in Table 6.

TABLE 6 Illustrative Aromatic Bisphenol Polycarbonates VI EntryStructure R³ R³ n′ n VIa

— — 0 0 VIb

CH₃ CH₃ 1 1 VIc

— — 0 0 VId

Cl Cl 2 2 VIe

Br Br 1 1 VIf

— — 0 0 VIg

— — 0 0 VIh

Et — 1 0 VIi

Et Et 1 1 VIj

— — 0 0 VIk

— — 0 0 VIl

— — 0 0 VIm

— — 0 0 VIn

— — 0 0 VIo

— — 0 0 VIp

— — 0 0 VIq

CH₃ CH₃ 2 2 VIr

CH₃ CH₃ 2 2 VIs

— — 0 0 VIt

— — 0 0 VIu

— — 0 0

In addition, copolycarbonates suitable for use according to one or moreaspects of the disclosure are illustrated by polycarbonate materialscomprising two or more of the structural units shown in illustrativeEntries VIa-VIu, for example a copolycarbonate comprising bothstructural units VIa (bisphenol A polycarbonate) and VIf (m,p-bisphenolA polycarbonate) within the same polymeric material.

Other species which may be used to activate a hydroxyl group of amonomeric polyol toward displacement by a bisphenol phenolate speciesinclude monomeric dialkyl carbonates such as dimethyl carbonate anddiethyl carbonate, aromatic carbonates such as diphenyl carbonate,aliphatic oxalates such as dimethyl oxalate and diethyl oxalate,aromatic oxalates such as diphenyl oxalate, and phosgene equivalentssuch as carbonyl diimidazole and hexachloroacetone. When one or more ofsuch other activating agents is employed instead of an oligomeric orpolymeric polycarbonate, the monomeric polyol(s) and the aromaticbisphenol(s) may be reacted under conditions similar to those describedin the Experimental Part of this disclosure, but may advantageously alsoinclude an additional step in which either or both of the monomericpolyol and the bisphenol is first reacted with the activating chemicalto form ester groups, aliphatic carbonate groups, aromatic carbonategroups, mixed aliphatic and aromatic carbonate groups and/or a mixturetwo or more of the foregoing carbonate groups. The initial reaction withthe activating chemical may be carried out at lower temperature than thesubsequent conversion to the oligomeric polyol composition, for instanceof about 15° C. or greater, about 25° C. or greater, about 50° C. orgreater, or about 75° C. or greater and about 250° C. or less, about200° C. or less, about 175° C. or less, or about 150° C. or less.Monomeric polyols include polyols disclosed herein.

There is disclosed a method of making an oligomeric polyol compositionwherein the activating agent is a component of a polyhydroxylatedaromatic moiety an aromatic bisphenol, moiety, is a component of apolyol moiety, is a component of both a polyhydroxylated aromaticmoiety, an aromatic bisphenol, moiety and a polyol moiety, or is presentas an independent reactant.

There is disclosed a method of making an oligomeric polyol compositioncomprising contacting one or more polyhydroxylated aromatic, aromaticbisphenol, moieties with one or more polyol moieties in the presence ofat least one activating agent and an effective amount of at least one ofa catalyst, a promoter or a mixture thereof. The contacting is carriedout at a temperature sufficient to cause formation of an oligomericnetwork linked to a plurality of peripheral groups. The oligomericnetwork comprises residues of at least one polyhydroxylated aromaticcompound aromatic bisphenol, and residues of at least one polyol. Atleast a portion of the peripheral groups comprise a residue of amonomeric polyol and/or a residue of the polyhydroxylated aromaticcompound, or the an aromatic bisphenol. The product oligomeric polyolcomposition may be used in a variety of applications, such aspolyurethane preparation, without a purification step.

There is disclosed a method of making an oligomeric polyol compositionin which one or more polyhydroxylated aromatic, diphenol, or aromaticbisphenols polycarbonates serves both as the source of thepolyhydroxylated aromatic, diphenol or aromatic bisphenol, moieties andas the source of the activating agent. The polyhydroxylated aromaticresidues may serve as the source of reactive aromatic hydroxyl and/orphenolate groups, and the carbonate units of the polycarbonate may serveas the activating agent which renders one or more hydroxy groups of thepolyol moieties susceptible to aromatic ether formation withpolyhydroxylated aromatic moieties. By way of example, apolyhydroxylated aromatic polycarbonate may be heated in the presence ofa catalyst together with a polyol comprising at least three hydroxylgroups at a temperature sufficient to cause the formation of mixedcarbonate linkages between polyhydroxylated aromatic polycarbonatemoieties of lower molecular weight than the polycarbonate used as theinitial starting material. The mixed carbonate linkages may lose carbondioxide and form aromatic ether linkages between a polycarbonate moietyand the residue of the polyol participating in the mixed carbonatelinkage. These mixed aromatic carbonate linkages may undergo furtherexchange with hydroxyl groups of the polyol or residues thereof to formcarbonate linkages not including a participating polyhydroxylatedaromatic moiety, for example a carbonate linkage between a first polyola (or a first polyol residue) and a second polyol (or a second polyolresidue). As the reaction between the polycarbonate and the polyolcontinues the concentration of aromatic ether linkages and carbonatelinkages not including a participating polyhydroxylated aromatic moietyincreases as molecular weight of the remaining polycarbonate moietiesdecreases. Those of ordinary skill in the art will understand that whena sufficient quantity of the polyol is used, essentially all of thecarbonate linkages in polycarbonate with be converted into carbondioxide or be converted into mixed carbonates, or carbonates between oneor more polyol residues. The product oligomeric polyol composition maycomprise a statistical mixture of products resulting from chain scissionof the polycarbonate starting material and include a substantial amountof free polyhydroxylated aromatic monomer and/or polycarbonate oligomersas well as unconsumed monomeric polyol and catalyst.

There is disclosed a method of making an oligomeric polyol compositionas just described, but substituting a promotor for the catalyst. Forexample, one or more monomeric polyhydroxylated amines comprising one ormore tertiary amines may serve as the promoter. Monomericpolyhydroxylated amines comprising one or more tertiary amines areillustrated by monomeric polyols Vf-Vm and Vu disclosed in Table 5herein. While the tertiary amine groups may survive the formation of theoligomeric polyol composition, the monomeric polyhydroxylated amine maybe incorporated via its hydroxy groups into the oligomeric polyol andconsumed as a result. It is noteworthy that oligomeric polyolscomprising residues of polyhydroxylated amines comprising tertiary aminegroups may serve as amine catalysts.

The process for making the oligomeric polyols may be performed at atemperature at which the oligomeric polyol is formed. The process formaking the oligomeric polyols may be performed at a temperature of about80° C. or greater, about 120° C. or greater or about 160° C. or greater.The process for making the oligomeric polyols may be performed at atemperature of about 220° C. or less, about 180° C. or less or about160° C. or less. The process for making the oligomeric polyols may beperformed for a sufficient time to form the oligomeric polyols. Suchreaction times may about 10 minutes or greater, about 45 minutes orgreater or about 90 minutes or greater. Such reaction times may about180 minutes or less, about 130 minutes or less or about 90 minutes orless. The molar ratio of the polyhydroxylated aromatic compounds topolyols is chosen such that physical and chemical properties of theoligomeric polyol may be tuned as needed. For example, the crosslinkdensity within the oligomeric polyol may be varied by varying the ratioof polyhydroxylated aromatic compounds to polyols. The molar ratio ofthe polyhydroxylated aromatic compounds to polyols may be about 3:1 orless, about 1.5:1 or less or about 1:1 or less. The molar ratio of thepolyhydroxylated aromatic compounds to polyols may be about 0.25:1 orgreater, about 0.6:1 or greater or about 1:1 or greater. Where acatalyst is present, any catalyst that is effective in causing theformation of the oligomeric network may be used. The catalyst may bepresent in an amount based on the weight of the reaction mixture ofabout 1 percent by weight or greater, about 5 percent by weight orgreater, or about 9 percent by weight or greater. The catalyst may bepresent in an amount based on the weight of the reaction mixture ofabout 25 percent by weight or less, about 15 percent by weight or less,or about 9 percent by weight or less. Where a promoter is present, anypromoter that is effective in causing the formation of the oligomericnetwork may be used. The promoter may act to solubilize and/orcompatibilize reactants used to create the oligomeric polyol and enhancereaction rates of chemical transformations that result in the formationof the oligomeric polyol. The promoter may be present in an amount basedon the weight of the reaction mixture of about 1 percent by weight orgreater, about 5 percent by weight or greater, or about 9 percent byweight or greater. The promoter may be present in an amount based on theweight of the reaction mixture of about 25 percent by weight or less,about 15 percent by weight or less, or about 9 percent by weight orless. The process may be performed wherein the polyol is at least onepolyhydroxylated amine having a tertiary amine. The tertiary amine canfunction as a catalyst and/or promoter. Where the process is performedwherein the polyol is at least one polyhydroxylated amine having atertiary amine group the polyhydroxylated amine having a tertiary aminegroup may be present in an amount of about 1 percent by weight orgreater, about 5 percent by weight or greater or about 9 percent byweight or greater based on the total weight of the reactants used toform the oligomeric polyol. Where the process is performed wherein thepolyol is at least one polyhydroxylated amine having a tertiary aminegroup, the polyhydroxylated amine having a tertiary amine group may bepresent in an amount of about 30 percent by weight or less, about 20percent by weight or less or about 9 percent by weight or less based onthe total weight of the reactants used to form the oligomeric polyol.

The oligomeric polyol may be prepared using at least two polyols onecontaining no amines and one containing a tertiary amine wherein thepolyol containing a tertiary amine can function as the catalyst. Forthis process the ratio of polyol to polyol containing a tertiary aminecan be any ratio that results in formation of the desired oligomericpolyol. The molar ratio of the polyol without an amine to polyolscontaining a tertiary amine may be about 2:1 or greater, about 4:1 orgreater or about 10:1 or greater. The molar ratio of the polyol withoutan amine to polyols containing a tertiary amine may be about 25:1 orless, about 15:1 or less or about 10:1 or less.

There are disclosed oligomeric polyol compositions which are liquids attwenty-five degrees centigrade, thirty-five degrees centigrade, fiftydegrees centigrade, or seventy-five degrees centigrade, and having aviscosity at 150 degrees Fahrenheit in a range from about 1000 cps, toabout 20000 cps, or about 40,000 cps.

There are disclosed oligomeric polyol compositions useful in thepreparation of novel polyurethane materials having excellent physicalproperties. The polyurethane materials and articles containing them maybe prepared using the techniques disclosed herein as well asart-recognized polyurethane polymer preparation and processingtechniques such as those disclosed in E. N. Doyle's The Development andUse of Polyurethane Products (McGraw-Hill, Inc. 1971), Saunders' et al.Polyurethanes Chemistry and Technology, Parts I-II (IntersciencePublishers), Saunders' Organic Polymer Chemistry (Chapman and Hall), J.M. Burst's Developments in Polyurethanes (Applied Science Publishers)and the Kirk Othmer Encyclopedia of Chemical Technology which areincorporated herein by reference in their entirety for all purposes.

When reacted with one or more polyisocyanates or polyisocyanateequivalents the oligomeric polyol compositions are converted intopolyurethanes with superior strength, hardness and moldability whencompared to analogous polyurethanes not incorporating such oligomericpolyol compositions. In addition, polyurethane-forming formulationscomprising one or more of the oligomeric polyol compositions disclosedherein exhibit less intense reaction exotherms during curing than doanalogous polyurethane-forming formulations lacking such oligomericpolyol compositions. Polyurethanes prepared from the oligomeric polyolsdisclosed herein exhibit excellent shrinkage resistance.

The oligomeric polyol compositions disclosed herein can be employed asin an easy to use A plus B polyurethane-forming formulation; component Acomprising one or more polyisocyanates or polyisocyanate equivalents andcomponent B comprising the oligomeric polyol composition. Component Bmay be a mixture of one or more of the oligomeric polyol compositionsdisclosed herein, and may contain one or more art recognized componentssuch as polyurethane catalysts, mold release agents, additional polyols,to name a few such art recognized components. Component A may contain apolyisocyanate prepolymer and/or one or more polyisocyanates, orcomponent A may comprise one or more polyisocyanate prepolymers and beessentially free of polyisocyanates. Such A plus B polymer systemsprovide a useful alternative to unsaturated polyester systems used inSMC, BMC and RTM molding, and epoxy systems used in casting and RTM.Because the oligomeric polyol compositions typically have a relativelylow viscosity under normal processing temperatures, they may be combinedwith one or more polyisocyanates and/or polyisocyanate prepolymers andinjected at low pressure and moderate temperatures eliminating the needfor expensive hydraulic presses and steel tooling such as are used inthermoplastic injection molding, BMC and SMC. Low cost aluminum toolingor even gel-coat FRP tooling may be used advantageously due to the lowinjection pressure needed to fill the mold and the relatively lowexotherm observed when the oligomeric polyols are reacted withpolyisocyanates. As will be appreciated by those of ordinary skill inthe art, significant advantages may attend the use of low cost toolingand processing equipment. Ease of processing during molding for example,will enhance the attractiveness of polyurethanes comprising structuralunits derived from oligomeric polyols relative to harder to processthermoplastics.

Polyurethane-forming formulations comprising the oligomeric polyolcompositions disclosed herein may be processed into molded polyurethanecontaining parts using one or more of Reaction Injection Molding (RIM),Compression Molding, Resin Transfer Molding, Poured Open Molding andSprayed Open Molding to name a few.

In one aspect, the oligomeric polyols disclosed herein may beincorporated into polyurethane elastomer precursor formulations whichprovide for rapid set up times to product polyurethanes having Young'smoduli below 50,000 psi while having excellent mold releasecharacteristics.

There is disclosed an oligomeric polyol composition which may be reactedwith a polyisocyanate or residue thereof having structure VII

wherein R⁴ is a hydrocarbyl group and m is an integer, to form usefulpolyurethane materials.

The isocyanate functional components can be in the form of isocyanatefunctional prepolymers, monomers or oligomers having on average greaterthan 1 isocyanate group, and preferably 2 or more isocyanate groups. Theisocyanate prepolymers can by any prepolymers prepared by reaction of anisocyanate functional compound with one or more compounds having onaverage more than one isocyanate reactive functional groups, such ashydroxyl, amine, thiol, carboxyl and the like, under conditions suchthat the prepolymers prepared have on average more than one isocyanatemoiety (group) per molecule. The isocyanate functional components arepresent in the curable composition in a sufficient amount to form acured component when exposed to curing conditions. The isocyanatefunctional component is present in the curable composition in asufficient amount to form a cured component when exposed to curingconditions. Exemplary polyisocyanates useful in the invention and inpreparing isocyanate functional prepolymers include any aliphatic,cycloaliphatic, araliphatic, heterocyclic or aromatic polyisocyanates,or mixtures thereof. The polyisocyanates used may have an averageisocyanate functionality of about 2.0 or greater and an equivalentweight of about 80 or greater. The isocyanate functionality of thepolyisocyanates may be about 2.0 or greater, about 2.2 or greater, orabout 2.4 or greater; and may be about 4.0 or less, about 3.5 or less,or about 3.0 or less. Higher functionality may be used, but may causeexcessive cross-linking and result in a composition which is too viscousto handle and apply easily, and can cause the cured composition to betoo brittle. The equivalent weight of the polyisocyanates may be about80 or greater, about 110 or greater, or about 120 or greater; and may beabout 300 or less, about 250 or less, or about 200 or less. Exemplaryaliphatic polyisocyanates include those disclosed by Wu, U.S. Pat. No.6,512,033 at column 3, line 3 to line 49, incorporated herein byreference. Exemplary aliphatic isocyanates include, isophoronediisocyanate, tetramethylxylene diisocyanate, 1,6-hexa-methylenediisocyanate and oligomeric or polymeric derivatives thereof,bis(4-isocyanato-cylohexyl)methane, and trimethyl hexamethylenediisocyanate. The aliphatic isocyanates may be hexamethylenediisocyanate and oligomeric and polymeric derivatives thereof. Examplesof aliphatic isocyanates include trimers of hexamethylene diisocyanate,such as those available from Bayer under the trademark and designationDESMODUR N3300, DESMODUR N3400, DESMODUR N-100. Exemplary aromaticpolyisocyanates may include those disclosed by Wu, U.S. Pat. No.6,512,033 at column 3, line 3 to line 49, incorporated herein byreference. Aromatic isocyanates may include diphenylmethanediisocyanate, toluene diisocyanate and polymeric derivatives thereof.One isocyanate is diphenylmethane diisocyanate. Oligomeric aromaticpolyisocyanates useful include those available from The Dow ChemicalCompany under the trademarks PAPI and VORANATE, such as VORANTE M220,PAPI 27 and PAPI 20 polymeric isocyanates.

There is disclosed an oligomeric polyol composition which may be reactedwith a polyisocyanate or residue thereof having structure VII

wherein R⁴ is a C₂-C₃₀ aliphatic radical, a C₅-C₂₀ cycloaliphaticradical, or a C₆-C₃₀ aromatic radical and m is an integer from 2 to 6,to provide a polyurethane material.

Additionally, R⁴ is a C₂-C₂₅ aliphatic radical, a C₅-C₁₅ cycloaliphaticradical, or a C₆-C₂₅ aromatic radical and m is an integer 2 or greaterand 4 or less, or 3 or less.

Further, R⁴ is a C₂-C₁₇ aliphatic radical, a C₅-C₁₃ cycloaliphaticradical, or a C₆-C₂₂ aromatic radical and m is an integer 2 or greaterand 3 or less.

Specific examples of polyisocyanates having structure VII and suitablefor incorporation into polyurethanes are given in Table 7 and includealiphatic polyisocyanates VIIa-VIIe, cycloaliphatic polyisocyanatesVIIf-VIIk, and aromatic polyisocyanates VII-VIIp.

TABLE 7 Illustrative Polyisocyanates VIl Entry Structure R⁴ m VIIa

(CH₂)₆ 2 VIIb

(CH₂)₁₀ 2 VIIc

See Structure 2 VIId

See Structure 4 VIIe

See Structure 2 VIIf

See Structure 2 VIIg

See Structure 2 VIIh

See Structure 3 VIIi

See Structure 2 VIIj

See Structure 2 VIIk

See Structure 2 VIIl

See Structure 2 VIIm

See Structure 2 VIIn

See Structure 2 VIIo

See Structure 3 VIIp

See Structure 3

There is disclosed a polyurethane material which may obtained by mixingone or more polyisocyanates, for example polyisocyanates VIII (MDI) andVIIn (TDI), or a latent form thereof such as a prepolymer or a blockedderivative, with the oligomeric polyol composition as the crude reactionproduct in which it is formed, for example a crude reaction productobtained by contacting bisphenol A polycarbonate powder (100 grams) witha mixture of polyols Va (100 grans) and Vf (20 grams) at a temperaturein a range from about 150 degrees centigrade to about 180 degreescentigrade for a period of one to three hours to provide a productmixture comprising an oligomeric polyol component comprising peripheralgroups Ia and Ig bound to an oligomeric network comprising structuralunits derived from bisphenol A polycarbonate and polyols Va and Vf. Thepolyisocyanates may be mixed with the oligomeric polyol composition inamounts such that there is a slight excess of hydroxyl groups relativeto isocyanate groups, thus assuring complete consumption of isocyanatesVIII and VIIn as the oligomeric polyol composition is converted into apolyurethane. In the example just given, the oligomeric polyolcomposition as produced may contain unbound monomeric polyols Va and Vfas well as free bisphenol A. The complexity of the oligomeric polyolcomposition notwithstanding, such compositions can be converted touseful polyurethane products without an intervening purification step.It may be useful to subject the oligomeric polyol composition to apurification step prior to its conversion to a polyurethane. Suitablepurification steps may include filtration, recrystallization, zonerefining and trituration, for example.

Disclosed is a composition comprising; in one part a) a polyisocyanate;and b) in a second part an oligomeric polyol as claimed herein; whereinwhen the first part and the second part are contacted and thecomposition cures.

In preparing the cured polyurethanes one or more second polyols may bepresent. The second polyol is one or more of a polyalkylene oxide etherbased polyol, a polyester polyol, a polyacrylate polyol or apolycarbonate polyol. Exemplary classes of polyols include polyetherpolyols, polyarylene ether polyols, polyester polyols, poly(alkylenecarbonate)polyols, hydroxyl containing polythioethers and mixturesthereof. Polyether polyols may contain one or more alkylene oxide unitsin the backbone of the polyol. Exemplary alkylene oxide units areethylene oxide, propylene oxide, butylene oxide and mixtures thereof.The alkylene oxides can contain straight or branched chain alkyleneunits. The polyol may contain propylene oxide units, ethylene oxideunits or a mixture thereof. Where a mixture of alkylene oxide units iscontained in a polyol, the different units can be randomly arranged orarranged in blocks of each alkylene oxide. The polyol may comprisepropylene oxide chains with ethylene oxide chains capping the polyol.The polyols may be a mixture of diols and triols. The individual polyolsmay have a functionality of about 1.9 or greater, about 1.95 or greater,or about 2.0 or greater; and may be about 6.0 or less, about 4.0 orless, about 3.5 or less, or about 3.0 or less. The equivalent weight ofthe second polyols may be about 200 or greater, about 500 or greater, orabout 1,000 or greater; and may be about 5,000 or less, about 3,000 orless, or about 2,500 or less. The second polyols may be located in thesecond part of a curable polyurethane composition. The second polyolsmay be present in the composition in an amount of about 2 percent byweight or greater, about 10 percent by weight or greater or about 20percent by weight or greater based on either the total weight of theoligomeric polyol composition, the total weight of a curable compositioncomprising in one part a) a polyisocyanate; and b) in a second part anoligomeric polyol, or the weight of either the polyisocyanate componentor the oligomeric polyol component of the curable composition. Thesecond polyol may be present in the composition in an amount of about 35percent by weight or less, about 15 percent by weight or less or about 5percent by weight or less based on either the total weight of theoligomeric polyol composition, the total weight of a curable compositioncomprising in one part a) a polyisocyanate; and b) in a second part anoligomeric polyol, or the weight of either the polyisocyanate componentor the oligomeric polyol component of the curable composition.

The curable compositions may further comprise one or more low molecularweight compounds having two or more isocyanate reactive groups and ahydrocarbon backbone wherein the backbone may further comprise one ormore heteroatoms. Such low molecular weight compounds may be chainextenders, such compounds are difunctional, or crosslinkers, havinggreater than two active hydrogen groups per compound. The heteroatoms inthe backbone may be oxygen, sulfur, nitrogen or a mixture thereof;oxygen, nitrogen or a mixture thereof; or oxygen, which is mostpreferred. The molecular weight of the low molecular weight compound maybe about 120 or less or about 100 or less. The low molecular weightcompound may comprise one or more multifunctional alcohols,multifunctional alkanol amines, one or more adducts of multifunctionalalcohol and an alkylene oxide, one or more adducts of a multifunctionalalkanol amine and an alkylene oxide or a mixture thereof. Exemplarymultifunctional alcohols and multifunctional alkanol amines are ethanediol, propane diol, butane diol, hexane diol, heptane diol, octane diol,glycerin, trimethylol propane, pentaerythritol, neopentyl glycol,ethanol amines (diethanol amine, triethanol amine) and propanol amines(di-isopropanol amine, tri-isopropanol amine) and the like. Blends ofvarious low molecular weight compounds may be used. The low molecularcompound may be located in the second part. The low molecular weightcompound may be present in the composition in an amount of about 2percent by weight or greater, about 3 percent by weight or greater orabout 4.0 percent by weight or greater. The low molecular weightcompound is present in the composition in an amount of about 16 percentby weight or less, about 12 percent by weight or less or about 10percent by weight or less.

The second part may comprise a catalyst for the reaction of hydroxylgroups with isocyanate groups. Among exemplary catalysts are organotincompounds, metal alkanoates, and tertiary amines. Mixtures of classes ofcatalysts may be used, such as a mixture of a tertiary amine and one ormore of organotin compounds or metal alkanoates. Such a mixture mayinclude tertiary amines, such as dimorpholino diethyl ether, and a metalalkanoate, such as bismuth octoate. Included in organotin compounds arealkyl tin oxides, stannous alkanoates, dialkyl tin carboxylates and tinmercaptides. Stannous alkanoates include stannous octoate. Alkyl tinoxides include dialkyl tin oxides, such as dibutyl tin oxide and itsderivatives. Exemplary organotin compounds are dialkyltin dicarboxylatesand dialkyttin dimercaptides. Dialkyl tin dicarboxylates with lowertotal carbon atoms are preferred as they are more active catalysts inthe compositions. Exemplary dialkyl dicarboxylates include1,1-dimethyttin dilaurate, 1,1-dibutyltin diacetate and 1,1-dimethyldimaleate. Preferred metal alkanoates include bismuth octoate or bismuthneodecanoate. The organo tin compounds or metal alkanoates may bepresent in an amount of about 60 parts per million or greater based onthe weight of the composition, about 120 parts by million or greater.The organo tin compounds or metal alkanoates may be present in an amountof about 1.0 percent or less based on the weight of the composition,about 0.5 percent by weight or less or about 0.2 percent by weight orless. Exemplary tertiary amine catalysts include dimorpholinodialkylether, a di((dialkyl-morpholino)alkyl)ether,bis-(2-dimethylaminoethyl)ether, triethylene diamine,pentamethyldi-ethylene triamine, N,N-dimethylcyclohexylamine,N,N-dimethyl piperazine, 4-methoxyethyl morpholine, N-methylmorpholine,N-ethyl morpholine, diazabicyclo compounds and mixtures thereof. Anexemplary dimorpholinodialkyl ether is dimorpholinodiethyl ether. Anexemplary di((dialkylmorpholino)alkyl)ether is(di-(2-(3,5-dimethylmorpholino)ethyl)-ether). Diazabicyclo compounds arecompounds which have diazobicyclo structures. Exemplary diazabicyclocompounds include diazabicycloalkanes and diazabicyclo alkene salts.Exemplary diazabicycloalkanes include diazabicyclooctane, available fromAir Products under the trademark and designations, DABCO, DABCO WT,DABCO DC 1, DABCO DC 2, and DABCO DC 21. Diazabicycloalkene saltsinclude diazabicycloundecene in the phenolate, ethylhexoate, oleate andformiate salt forms, available from Air Products under the trademark anddesignations, POLYCAT SA 1, POLYCAT SA 1/10, POLYCAT SA 102 and POLYCATSA 610. Tertiary amines may be employed in an amount, based on theweight of the composition of about 0.01 percent by weight or greater,about 0.05 percent by weight or greater, about 0.1 percent by weight orgreater or about 0.2 percent by weight or greater and about 2.0 percentby weight or less about 1.5 percent by weight or less, or about 1.2percent by weight or less.

One or both of parts may contain a filler. Fillers are added for avariety of reasons and one or more types of fillers may be utilized inthe composition. Fillers may be added to reinforce the composition, toimpart the appropriate viscosity and rheology and to strike a balancebetween cost and the desired properties of the composition and the partsof the composition. Reinforcing fillers, such as one or more carbonblacks, one or more clays or non-pigmented fillers, one or morethixotropes or combinations thereof may be used. Such fillers are usedin a sufficient amount to impart an acceptable balance of viscosity andcost to the formulation and to achieve the desired properties of thecomposition. Among fillers useful for this purpose are clays, untreatedand treated talc, and calcium carbonates. Preferred clays useful in theinvention include kaolin, surface treated kaolin, calcined kaolin,aluminum silicates and surface treated anhydrous aluminum silicates.Kaolin is also known as Kaolinite and comprises compounds represented bythe chemical formula Al₂Si₂O₅ (OH)₄, and it most often occurs asclay-sized, plate like, hexagonally shaped crystals. The clays can beused in any form which facilitates formulation of a composition havingthe desired properties. The composition may further comprise fillerswhich function as a thixotrope (rheological additive). Such thixotropesare well known to those skilled in the art and include fumed silica andthe like. Preferred fumed silicas include organically modified fumedsilicas. The thixotrope may be added to the composition in a sufficientamount to give the desired rheological properties. Additional suitablefillers include glass flake, glass fibers carbon fiber and basalt fiber.

The compositions may further comprise a plasticizer commonly used inpolyurethane compositions. The composition may contain plasticizers inboth components. Exemplary plasticizers include straight and branchedalkylphthalates, such as diisononyl phthalate, dioctyl phthalate anddibutyl phthalate, a partially hydrogenated terpene commerciallyavailable as “HB-40”, trioctyl phosphate, alkylsulfonic acid esters ofphenol, toluene-sulfamide, adipic acid esters, castor oil, xylene,1-methyl-2-pyrrolidinone and toluene. Exemplary plasticizers arebranched plasticizers, such as branched chain alkyl phthalates forexample di-isononyl phthalates (available under the Trademark PLATINOL Nfrom BASF. The amount of plasticizer used is that amount sufficient togive the desired rheological properties and disperse the components inthe curable composition. The plasticizer is present in about 1 percentby weight or greater of the composition, about 5 percent by weight orgreater, or about 10 percent by weight or greater. The plasticizer maybe present in about 50 percent by weight or less of the composition orabout 40 percent by weight or less.

Other components commonly used in curable compositions may be used inthe compositions. Such materials are well known to those skilled in theart and may include ultraviolet stabilizers and antioxidants and thelike.

Experimental Part

Examples describing the preparation of oligomeric polyol compositionsand their conversion into polyurethane materials are presented.Structures for representative polyols comprising at least three hydroxylgroups and polyhydroxylated amines are presented in Table 5 and thestructures of polyols Va and Vf are reproduced below.

Example 1 Preparation of Oligomeric Polyol Composition

A 10-liter reaction vessel equipped with an overhead stirrer,thermometer/thermocouple port and optionally a nitrogen inlet wascharged with 100 parts of propoxylated pentaerythritol (PEP 450) and 20parts of Multranol 9181. The flask and contents were heated to 150° C.and polycarbonate powder, 100 parts was added portion-wise over a periodof about 2 hours. When addition of the polycarbonate was complete themixture was stirred at about 150° C. until gas evolution ceased(approximately 1 hour). The molten mixture solidified to a glassy brownsolid on cooling.

Analysis of this product oligomeric polyol composition using gelpermeation chromatography with UV detection indicated that significantchain scission of the polycarbonate had occurred. The gel permeationchromatogram exhibited a broad, bimodal peak in the 3,000 to 5000 MWrange and a relatively sharp peak indicative of free bisphenol A. TheFTIR spectrum of the product exhibited no absorption at 1770 cm-1indicative of the aromatic carbonate linkage. Instead, a mediumabsorbance at 1750 cm-1 was observed corresponding to aliphatic esterand/or carbonate groups. The oligomeric polyol composition was shown tocontain both aromatic and aliphatic hydroxyl groups. The productoligomeric polyol composition flowed freely when warmed (See Table 9)and did not appear to be highly crosslinked. The level of branchingpresent in the oligomeric polyol could not be determined with precisionowing to the complexity of the proton and carbon NMR spectra in theportions of the spectrum of interest. Polyurethane compositionscomprising the reaction product of the oligomeric polyol compositionwith a polyisocyanate exhibited DSC/DMA behavior consistent a singlephase polyurethane.

Examples 2-5

Following a procedure analogous to that described in Example 1 butvarying the relative amounts of each of the components affordedsimilarly constituted oligomeric polyol compositions. These compositionsare described in Table 8. It is to be noted that when lower amounts ofthe tertiary amine are employed (examples 3 and 4) the infrared spectrumexhibited a carbonyl absorption at 1770 cm⁻¹ indicating that at leastsome aromatic carbonate groups were present in the product oligomericpolyol composition.

TABLE 8 Oligomeric Polyol Compositions - Examples 2-5 PEP 450 BPA-PCMultranol 9181 FTIR vC═O Example (parts) (parts) (parts) cm−1 2 200 10020 1750 3 100 100 10 1770 (weak) 4 200 100 10 1770 (weak) 5 0 100 1001727

Example 6 Polyurethane Based on Oligomeric Polyol Composition

A polyurethane composition was made using as Component “B” of a two-partA+B formulation an oligomeric polyol composition made by combining 600grams of a tetra functional amine based monomeric polyol, Multranol 9181(Covestro), with 3000 grams of tetra functional polyether polyol,Pluracol 450 (BASF), and 3000 grams of 30,000 molecular weight BisphenolA polycarbonate, Lexan 105 (Sabic) in the manner described in Example 1above. Multranol 9181 contains tertiary amine groups and issubstantially free of primary and secondary amine groups. Pluracol 450is substantially free of amine groups. Each of Multranol 9181 andPluracol 450 contains four hydroxyl groups per molecule. This productoligomeric polyol composition may be referred to herein asPEP450/9181/PC105 and had the viscosity/temperature characteristicsgiven in Table 9.

TABLE 9 Viscosity Profile of PEP450/9181/PC105 Oligomeric PolyolComposition Viscosity Temp Deg F. Viscosity CPS 130 23520 140 11980 1507128 160 4404 170 3044 180 2164 190 1515 200 1116

The oligomeric polyol composition (Component B, “B-Side”) was mixed withan isocyanate (Component A, “A Side) consisting of a modified polymericdiphenylmethane diisocyanate (MDI) Baydur 486 (Covestro), in astochiometric equivalent amount using a cast elastomer dispensingmachine equipped with a dynamic mixhead. The pumping conditions were asfollows:

Pumping Conditions Ratio Temperature Deg F. A-Side Baydur 486 42.8% 150B-Side PEP450/9181/PC105 57.2% 190

The resulting mixture was open poured into a 12 inch by 12 inch by⅜-inch mold heated to 150 F and allowed to cure. The resulting gel timewas 45 seconds and the peak exotherm was 230 F. The finished plaque wasmachined to suitable test specimens according to ASTM D790 and testedfor flexural strength and modulus. The resulting values were:

Flex Strength (psi) 17,780 ASTM D790 Flex Modulus (psi) 465,120 ASTMD790

In addition to the plaque sample a test part was made by open pouringthe mixture into a silicone rubber mold. The part was easily removedfrom the mold and had excellent surface appearance and mold replicationas shown in FIG. 1.

Comparative Example 1 Polyurethane without Oligomeric Polyol Composition

A polyurethane composition was made using as the “B” side a mixture of600 grams of Multranol 9181 and 3000 grams of Pluracol 450 without anyadded polycarbonate. This Multranol 9181/Pluracol 450 mixture had theviscosity/temperature characteristics given in Table 10.

TABLE 10 Viscosity Profile of PEP 450 - Multranol 9181 Mixture ViscosityTemp Deg F. Viscosity CPS 100 633 110 442 120 307 130 193 140 129 150 89160 61 170 44 180 30 190 22

The mixture of Multranol 9181 and PEP 450 was used as the “B” componentof an A+B polyurethane formulation. The Multranol 9181-PEP 450 Bcomponent was mixed with an isocyanate “A-Side” component consisting ofa modified polymeric diphenylmethane diisocyanate (MDI) (Baydur 486 fromCovestro) in a stochiometric equivalent amount using a cast elastomerdispensing machine equipped with a dynamic mixhead. The pumpingconditions were as follows:

Pumping Conditions Volumetric Ratio Temperature F. A-Side Baydur 48658.3% 150 B-Side PEP450/9181 41.7% 160

The resulting mixture was open poured into a 12 inch by 12 inch by⅜-inch mold as in Example 11 and cured. The gel time observed was 20seconds and a peak exotherm was 265 F. The finished plaque was machinedto suitable test specimens according to ASTM D790 and tested forflexural strength and modulus. The resulting values were:

Flex Strength (psi) 20,506 ASTM D790 Flex Modulus (psi) 361,244 ASTMD790

In addition to the plaque sample, a test part was made by open pouringthe mixture into a silicone rubber mold. The part was difficult toremove from the mold and had rough and irregular surface appearance andpoor mold replication as shown in FIG. 2.

Data obtained for the polyurethane of Example 6 and the polyurethane ofComparative Example 1 are assembled below and in FIG. 3 for convenienceof comparison. The use of the oligomeric polyol composition resulted inlower exotherm and higher flexural modulus. The lower exotherm can allowthe use of lower cost fiber reinforced gel coat tooling and the higherstiffness can meet the needs of more demanding structural applications.The addition of the oligomeric polyol composition also resulted in asignificant improvement in the part appearance and in the moldreplication fidelity.

Polyurethane Gel Flex Composition Time Exotherm Strength Flex Modulus486/9181/PEP450/PC 45 sec. 230 F. 17,780 psi. 465,120 psi486/9181/PEP450. 20 sec. 265 F. 20,506 psi 361.244 psi

The invention claimed is:
 1. An oligomeric polyol compositioncomprising: (a) an oligomeric network comprising residues of at leastone polyhydroxylated aromatic compound and residues of at least onepolyol having more than three secondary hydroxyl groups; and (b) aplurality of peripheral groups each comprising one or more hydroxylgroups bound to the oligomeric network by a plurality of linking units,wherein at least a portion of the linking units are oxygen atoms ofhydrocarbyl ether linkages, carbonate linkages, or ester linkages;wherein the residues of the at least one polyol optionally comprises oneor more oxygen ether groups, one or more linking nitrogen atomscomprised within an alkylene chain, or both one or more oxygen ethergroups and one or more linking nitrogen atoms comprised within analkylene chain, wherein the oligomeric polyol composition exhibits aviscosity at 150° F. of 1000 to 40,000 cps.
 2. The composition accordingto claim 1, wherein at least a portion of the residues of at least onepolyhydroxylated aromatic compound comprises residues of at least onearomatic bisphenol.
 3. The composition according to claim 1, wherein atleast a portion of the linking units are carbonate linkages.
 4. Thecomposition according to claim 1, wherein at least a portion of theplurality of peripheral groups are aliphatic peripheral groupscomprising a residue of at least one monomeric aliphatic polyol, thealiphatic peripheral groups comprising at least two hydroxyl groups. 5.The composition according to claim 1, wherein the at least one polyolcontains one or more oxygen ether groups, one or more linking nitrogenatoms comprised within an alkylene chain, or both one or more oxygenether groups and one or more linking nitrogen atoms comprised within analkylene chain.
 6. The composition according to claim 5, wherein the atleast one polyol comprises both one or more oxygen ether groups and oneor more or linking nitrogen atoms comprised within an alkylene chain. 7.The composition according to claim 1, comprising residues of at leastone polyol which is a monomeric polyhydroxylated amine.
 8. Thecomposition according to claim 1, wherein at least a portion of theperipheral groups have:

wherein R¹ and R² are independently at each occurrence a hydrogen atom,or a hydrocarbyl group such that R¹ and R², either alone or together,comprise at least two hydroxyl groups; R³ is independently at eachoccurrence a non-carbon substituent or a hydrocarbyl group; W is a bondor a linking group; the variables n and n′ are independently an integerfrom 0 to 4; and X¹ is a linking unit joining peripheral group I, II orIII to oligomeric network Y¹, oligomeric network Y¹ comprising residuesof at least one aromatic bisphenol and residues of at least onemonomeric polyol having more than three secondary hydroxyl groups. 9.The composition according to claim 1, wherein at least a portion of theperipheral groups have structure I

wherein R¹ and R² are independently at each occurrence a hydrogen atom,a C₁-C₃₀ aliphatic radical, a C₅-C₃₀ cycloaliphatic radical, a C₆-C₃₀aromatic radical, or R¹ and R² together form a C₅-C₃₀ cycloaliphaticradical or a C₆-C₃₀ aromatic radical; with the proviso that R¹ and R²,either alone or together, comprise at least two hydroxyl groups; and X¹is a linking unit joining peripheral group I to oligomeric network Y¹,oligomeric network Y¹ comprising residues of at least one aromaticbisphenol and residues of at least one monomeric polyol having more thanthree secondary hydroxyl groups.
 10. The composition according to claim1, further comprising at least one polyhydroxylated aromatic compound.11. The composition according to claim 1, wherein a portion of the atleast one polyhydroxylated aromatic compound comprises bisphenol A. 12.A method of making the oligomeric polyol composition according to claim1, comprising: contacting one or more compositions containing one ormore polyhydroxylated aromatic moieties with one or more polyols havingmore than 3 secondary hydroxyl groups in the presence of at least oneactivating agent and an effective amount of at least one of a catalyst,a promoter or a mixture thereof, at a temperature sufficient to causeformation the oligomeric network comprising residues of the one or morepolyhydroxylated aromatic moieties and residues of the one or morepolyols to provide the product oligomeric polyol composition.
 13. Amethod according to claim 12 wherein the one or more polyhydroxylatedaromatic moieties are derived from one or more polycarbonates.
 14. Amethod of making the oligomeric polyol composition according to claim 1,comprising: contacting one or more aromatic bisphenol moieties with oneor more monomeric polyols having more than 3 secondary hydroxyl groupsin the presence of at least one activating agent and an effective amountof at least one of a catalyst, a promoter or a mixture thereof, at atemperature sufficient to cause formation of an oligomeric networkcomprising residues of the one or more aromatic bisphenol moieties andresidues of the one or more monomeric polyols to provide a productoligomeric polyol composition.
 15. A method according to claim 14wherein the one or more aromatic bisphenol moieties are derived from oneor more polycarbonates.
 16. An oligomeric polyol composition accordingto claim 1 prepared by a method comprising: contacting one or morepolyhydroxylated aromatic moieties with one or more polyols having morethan 3 secondary hydroxyl groups in the presence of at least oneactivating agent and an effective amount of at least one of a catalyst,a promoter or a mixture thereof, at a temperature sufficient to causeformation of an oligomeric network comprising residues of the one ormore polyhydroxylated aromatic moieties and residues of the one or morepolyols to provide the product oligomeric polyol composition, whereinthe oligomeric polyol composition exhibits a viscosity at 150° F. of1000 to 40,000 cps.
 17. A composition according to claim 16 wherein theone or more polyhydroxylated aromatic moieties are derived from one ormore polycarbonates.
 18. An oligomeric polyol composition according toclaim 1 prepared by a method comprising: contacting one or more aromaticbisphenol moieties with one or more monomeric polyols having more than 3secondary hydroxyl groups in the presence of at least one activatingagent and an effective amount of at least one of a catalyst, a promoteror a mixture thereof, at a temperature sufficient to cause formation ofan oligomeric network comprising residues of the one or more aromaticbisphenol moieties and residues of the one or more monomeric polyols toprovide a product oligomeric polyol composition, wherein the oligomericpolyol composition exhibits a viscosity at 150° F. of 1000 to 40,000cps.
 19. A composition according to claim 18 wherein the one or morearomatic bisphenol moieties are derived from one or more polycarbonates.20. A composition according to claim 1 wherein the at least one polyolis tetrafunctional having 4 secondary hydroxyl groups.
 21. Apolyurethane composition prepared from the oligomeric polyol compositionaccording to claim 1; wherein urethane units are formed from reaction ofisocyanate moieties of one or more polyisocyanates and the hydroxylgroups of the peripheral groups, which exhibits heat distortiontemperatures in excess of 110 degrees centigrade, peak exotherms lessthan 250 degrees Fahrenheit during in-mold curing/polymerization,flexural strengths in excess of 10,000 psi and a flexural modulus inexcess of 400,000 psi.
 22. An article comprising the compositionaccording to claim 21 which exhibits a heat distortion temperature inexcess of 110 degrees centigrade, a flexural strength in excess of10,000 psi and a flexural moduli in excess of 400,000 psi.
 23. A moldedarticle comprising the composition according to claim 21 which exhibitsa heat distortion temperature in excess of 110 degrees centigrade, aflexural strength in excess of 10,000 psi and a flexural modulus inexcess of 400,000 psi.
 24. A method of making a polyurethanecomposition, comprising contacting the oligomeric polyol according toclaim 1 with one or more polyisocyanate moieties, optionally in thepresence of a catalyst, at a temperature sufficient to cause at least aportion of the hydroxyl groups of the peripheral groups to react withone or more isocyanate groups or latent isocyanate groups of thepolyisocyanate moieties to form a polyurethane product, wherein thepolyurethane composition exhibits a heat distortion temperature inexcess of 110 degrees centigrade, a peak exotherm less than 250 degreesFahrenheit during in-mold curing/polymerization, a flexural strength inexcess of 10,000 psi and a flexural modulus in excess of 400,000 psi.25. A method of making a molded article comprising: (a) mixing a firstreactant comprising one or more polyisocyanates or latentpolyisocyanates with a second reactant comprising the oligomeric polyolcomposition according to claim 1 to form a reactive mixture; (b)transferring the reactive mixture into a mold; and (c) curing thereactive mixture within the mold to afford a molded part; wherein duringstep (b) at least a portion of the hydroxyl groups of the peripheralgroups react with one or more isocyanate groups or latent isocyanategroups to form a polyurethane product.
 26. A composition comprising; inone part a) a polyisocyanate; and b) in a second part an oligomericpolyol according to claim 1; wherein when the first part and the secondpart are contacted the composition cures by reaction of at least aportion of the hydroxyl groups of the peripheral groups with thepolyisocyanate.